KR102203366B1 - Application solution for resist pattern coating - Google Patents
Application solution for resist pattern coating Download PDFInfo
- Publication number
- KR102203366B1 KR102203366B1 KR1020177004633A KR20177004633A KR102203366B1 KR 102203366 B1 KR102203366 B1 KR 102203366B1 KR 1020177004633 A KR1020177004633 A KR 1020177004633A KR 20177004633 A KR20177004633 A KR 20177004633A KR 102203366 B1 KR102203366 B1 KR 102203366B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- resist pattern
- coating
- alkyl group
- polymer
- Prior art date
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 210
- 239000011248 coating agent Substances 0.000 title claims abstract description 209
- -1 ketone compound Chemical class 0.000 claims abstract description 125
- 229920000642 polymer Polymers 0.000 claims abstract description 110
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 62
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 55
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 125000001424 substituent group Chemical group 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 125000006165 cyclic alkyl group Chemical group 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 78
- 239000000758 substrate Substances 0.000 claims description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 23
- 125000000962 organic group Chemical group 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000010408 film Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 56
- 239000000178 monomer Substances 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 15
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 9
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- 229940116333 ethyl lactate Drugs 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000001312 dry etching Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001459 lithography Methods 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 4
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 4
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- LDWLIXZSDPXYDR-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC(C=O)=CC(C(F)(F)F)=C1 LDWLIXZSDPXYDR-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 0 Cc1cc(C=O)cc(*)c1C(F)(F)F Chemical compound Cc1cc(C=O)cc(*)c1C(F)(F)F 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 2
- HANWHVWXFQSQGJ-UHFFFAOYSA-N 1-tetradecoxytetradecane Chemical compound CCCCCCCCCCCCCCOCCCCCCCCCCCCCC HANWHVWXFQSQGJ-UHFFFAOYSA-N 0.000 description 2
- TXYKVMGAIGVXFY-UHFFFAOYSA-N 1-undecoxyundecane Chemical compound CCCCCCCCCCCOCCCCCCCCCCC TXYKVMGAIGVXFY-UHFFFAOYSA-N 0.000 description 2
- HHBZZTKMMLDNDN-UHFFFAOYSA-N 2-butan-2-yloxybutane Chemical compound CCC(C)OC(C)CC HHBZZTKMMLDNDN-UHFFFAOYSA-N 0.000 description 2
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 description 2
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical class [H]C([H])([H])C([H])([H])O* 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical class [H]C([H])([H])O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000012487 rinsing solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- TZEUDSUHMOPLQM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxycyclohexane Chemical compound CC(C)(C)OC1CCCCC1 TZEUDSUHMOPLQM-UHFFFAOYSA-N 0.000 description 1
- AWCQPJGDROLAIF-UHFFFAOYSA-N (2-methylpropan-2-yl)oxycyclopentane Chemical compound CC(C)(C)OC1CCCC1 AWCQPJGDROLAIF-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- MIOPJNTWMNEORI-XVKPBYJWSA-N (R)-camphorsulfonic acid Chemical compound C1C[C@]2(CS(O)(=O)=O)C(=O)C[C@H]1C2(C)C MIOPJNTWMNEORI-XVKPBYJWSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
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Abstract
[과제] 신규한 레지스트 패턴 피복용 도포액을 제공한다.
[해결수단] A성분: 적어도 1개의 하이드록시기 또는 카르복시기를 함유하는 폴리머, B성분: A-SO3H(식 중, A는 탄소원자수 1 내지 16의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 방향족기, 또는 치환기를 가질 수도 있는 탄소원자수 4 내지 16의 지환식 기를 나타낸다.)로 표시되는 설폰산, 그리고 C성분: R1-O-R2 및/또는 R1-C(=O)-R2(식 중, R1은 탄소원자수 3 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타내고, R2는 탄소원자수 1 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타낸다.)로 표시되는 에테르 또는 케톤 화합물로 이루어진, 상기 폴리머를 용해가능한 유기용매를 포함하는 레지스트 패턴 피복용 도포액, 그리고 이 도포액을 이용하는 레지스트 패턴 혹은 반전 패턴의 형성방법.[Problem] To provide a novel coating solution for resist pattern coating.
[Solution] A component: a polymer containing at least one hydroxy group or carboxyl group, B component: A-SO 3 H (wherein, A is a linear or branched alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms , An aromatic group having at least one alkyl group or a fluorinated alkyl group as a substituent, or an alicyclic group having 4 to 16 carbon atoms which may have a substituent.), and a C component: R 1 -OR 2 and / Or R 1 -C (=O) -R 2 (In the formula, R 1 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 3 to 16 carbon atoms, and R 2 is a carbon atom number of 1 to 16 A coating solution for coating a resist pattern containing an organic solvent capable of dissolving the polymer, consisting of an ether or ketone compound represented by (representing a linear, branched or cyclic alkyl group or fluorinated alkyl group), and a resist using the coating solution A method of forming a pattern or inversion pattern.
Description
본 발명은, 레지스트 패턴의 폭 또는 직경을 축소시키는 것이 가능한, 레지스트 패턴 피복용 도포액에 관한 것이다. 나아가, 이 도포액을 이용한, 레지스트 패턴의 형성방법, 및 반전 패턴의 형성방법에 관한 것이다.The present invention relates to a coating liquid for coating a resist pattern capable of reducing the width or diameter of a resist pattern. Further, it relates to a method for forming a resist pattern and a method for forming a reverse pattern using this coating liquid.
반도체장치의 제조에 있어서, 레지스트 조성물을 이용한 리소그래피에 의한 미세가공이 행해지고 있다. 상기 미세가공은, 실리콘 웨이퍼 등의 반도체기판 상에 포토레지스트 조성물의 박막을 형성하고, 그 위에 디바이스의 패턴이 그려진 마스크패턴을 개재하여 자외선 등의 활성광선을 조사하고, 현상하여, 얻어진 포토레지스트 패턴을 보호막으로 하여 기판을 에칭처리함으로써, 기판 표면에, 상기 패턴에 대응하는 미세요철을 형성하는 가공법이다. 최근, 반도체 디바이스의 고집적도화가 진행되고, 사용되는 활성광선도 i선(파장 365nm), KrF 엑시머레이저(파장 248nm)로부터 ArF 엑시머레이저(파장 193nm)로 단파장화되고 있다.In the manufacture of a semiconductor device, microprocessing by lithography using a resist composition is performed. In the microprocessing, a photoresist pattern obtained by forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating active light such as ultraviolet rays through a mask pattern on which a device pattern is drawn thereon, and developing This is a processing method of forming a microrelief corresponding to the pattern on the surface of the substrate by etching the substrate using as a protective film. In recent years, high integration of semiconductor devices has progressed, and the active light used is also shortened from i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm) to ArF excimer laser (wavelength 193 nm).
그리고 현재, 향상된 미세가공기술인, EUV(극단자외선의 약칭, 파장 13.5nm) 노광을 채용한 리소그래피가 검토되고 있다. 그러나, 고출력의 EUV광원의 개발지연 등의 이유로, EUV노광을 채용한 리소그래피는 아직 실용화(양산화)에 도달하지 않았다.And now, lithography employing an improved microfabrication technology, EUV (short term for extreme ultraviolet, wavelength 13.5 nm), is being studied. However, for reasons such as a delay in the development of a high-power EUV light source, lithography employing EUV exposure has not yet reached practical use (mass production).
한편, 레지스트 패턴 축소화를 위한 재료를 레지스트 패턴 상에 도포하고, 해당 레지스트 패턴을 미세화(축소화)시키는 방법, 및 이를 위하여 사용되는 상기 도포재료가 알려져 있다(예를 들어, 특허문헌 1 내지 특허문헌 4). 이 방법을 채용함으로써, 이미 실용화되어 있는 ArF 엑시머레이저에 의한 노광을 채용한 리소그래피에 의해 제작한 레지스트 패턴을, 더욱 미세화하는 것이 가능해진다.On the other hand, a method of applying a material for reducing a resist pattern onto a resist pattern and miniaturizing (reducing) the resist pattern, and the coating material used for this are known (for example, Patent Documents 1 to 4 ). By employing this method, it becomes possible to further refine a resist pattern produced by lithography employing exposure with an ArF excimer laser that has already been put into practical use.
특허문헌 1에 기재되어 있는 수용성 수지를 함유하는 수용액(레지스트 패턴 축소화 재료)은, 유기용매와 비교했을 때 표면장력이 높은 물을 용매로 사용하는 점에서, 레지스트 패턴에 대한 도포성에 어려움이 있다. 이 때문에, 계면활성제를 첨가하거나, 또는 수용성의 알코올류를 물과 혼합하여 사용할 필요가 있다. 특허문헌 2에 기재되어 있는 레지스트 패턴 미세화 조성물은, 폴리머를 포함하지 않는 용액인 점에서, 미세화 대상인 레지스트 패턴의 형상에 의존하여, 미세화되는 비율에 격차가 생기기 쉽다. 특허문헌 3에 기재되어 있는 패턴 미세화 처리제는, 산발생제 성분을 함유하는 것이며, 이 패턴 미세화 처리제의 도포후에 행하는 베이크처리를 130℃ 이상의 높은 온도에서 행하거나, 또는 이 패턴 미세화 처리제의 도포후에 노광하는 공정을 추가하는 것이 요구되고 있다. 특허문헌 4에 기재되어 있는 미세패턴의 형성방법은, 네가티브형 현상 프로세스에 의해 형성된 레지스트 패턴을 협소화하는, 즉 이 레지스트 패턴 상에 피복막을 형성한 후, 가열함으로써 레지스트 패턴간의 간격인 스페이스폭을 줄이는 것을 목적으로 한다. 따라서, 이 문헌에 개시되는 상기 미세패턴의 형성방법은, 레지스트 패턴의 폭 또는 직경을 축소시키는 것을 목적으로 하지 않는다.The aqueous solution containing a water-soluble resin described in Patent Literature 1 (resist pattern reduction material) has difficulty in coating properties to a resist pattern in that it uses water having a high surface tension as a solvent compared to an organic solvent. For this reason, it is necessary to add a surfactant or to use a water-soluble alcohol mixed with water. Since the resist pattern refining composition described in Patent Literature 2 is a solution containing no polymer, it is easy to produce a variation in the ratio to be refined depending on the shape of the resist pattern to be refined. The pattern refinement treatment agent described in Patent Document 3 contains an acid generator component, and the baking treatment performed after the application of the pattern refinement treatment agent is performed at a high temperature of 130°C or higher, or exposure after application of the pattern refinement treatment agent. It is required to add a process to do it. The method of forming a fine pattern described in Patent Document 4 narrows the resist pattern formed by the negative developing process, that is, reduces the space width, which is the interval between the resist patterns, by heating after forming a coating film on the resist pattern. It is aimed at. Therefore, the method for forming a fine pattern disclosed in this document does not aim to reduce the width or diameter of the resist pattern.
본 발명은, 상기 과제를 해결하기 위하여 이루어진 것이며, 레지스트 패턴의 폭을 축소시키는 것이 가능한, 레지스트 패턴 피복용 도포액, 이 도포액을 이용한 레지스트 패턴의 형성방법, 및 이 도포액을 이용한 반전 패턴의 형성방법을 제공하는 것을 목적으로 한다.The present invention has been made in order to solve the above problems, and it is possible to reduce the width of the resist pattern, a coating solution for coating a resist pattern, a method of forming a resist pattern using the coating solution, and a reverse pattern using the coating solution. It aims to provide a method of formation.
본 발명의 제1 태양은,The first aspect of the present invention,
A성분: 적어도 1개의 하이드록시기 또는 카르복시기를 함유하는 폴리머,Component A: a polymer containing at least one hydroxy group or carboxyl group,
B성분: A-SO3H(식 중, A는 탄소원자수 1 내지 16의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 방향족기, 또는 치환기를 가질 수도 있는 탄소원자수 4 내지 16의 지환식 기를 나타낸다.)로 표시되는 설폰산, 그리고B component: A-SO 3 H (in the formula, A is a straight or branched alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms, an aromatic group having at least one alkyl group or a fluorinated alkyl group as a substituent, or a substituent Sulfonic acid represented by an alicyclic group having 4 to 16 carbon atoms which may be), and
C성분: R1-O-R2 및/또는 R1-C(=O)-R2(식 중, R1은 탄소원자수 3 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타내고, R2는 탄소원자수 1 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타낸다.)로 표시되는 화합물로 이루어진, 상기 폴리머를 용해가능한 유기용매,C component: R 1 -OR 2 and/or R 1 -C(=O)-R 2 (in the formula, R 1 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 3 to 16 carbon atoms, R 2 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms.), an organic solvent capable of dissolving the polymer;
를 포함하는 레지스트 패턴 피복용 도포액이다.It is a coating liquid for coating a resist pattern containing.
상기 A성분인 폴리머는, 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기를 추가로 함유할 수 있다.The polymer as the component A may further contain a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom.
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 상기 A성분인 폴리머는, 하기 식(A)로 표시되는 구조단위를 갖는 폴리머로 할 수 있다.The polymer which is the component A contained in the coating liquid for coating a resist pattern of the present invention can be a polymer having a structural unit represented by the following formula (A).
[화학식 1][Formula 1]
(식 중, R0은 수소원자 또는 메틸기를 나타내고,(In the formula, R 0 represents a hydrogen atom or a methyl group,
L은 적어도 1개의 치환기를 가질 수도 있는 2가의 방향족 기, -C(=O)-O-기 또는 -C(=O)-NH-기를 나타내고, 이 -C(=O)-O-기 또는 -C(=O)-NH-기의 탄소원자는 폴리머의 주쇄와 결합하는 것이며,L represents a divalent aromatic group that may have at least one substituent, a -C(=O)-O- group, or a -C(=O)-NH- group, and this -C(=O)-O- group or The carbon atom of the -C(=O)-NH- group is bonded to the main chain of the polymer,
X는 수소원자, 또는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기 혹은 알콕시기를 나타내고, 이 알킬기는 적어도 1개의 수소원자가 할로겐원자 또는 하이드록시기로 치환될 수도 있다.)X represents a hydrogen atom, or a linear or branched alkyl group or alkoxy group having 1 to 10 carbon atoms, and in this alkyl group, at least one hydrogen atom may be substituted with a halogen atom or a hydroxy group.)
단 상기 식(A)로 표시되는 구조단위를 갖는 폴리머는, 적어도 1개의 하이드록시기 또는 카르복시기를 함유하는 것이며, 나아가, 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기를 함유할 수 있다.However, the polymer having the structural unit represented by the above formula (A) contains at least one hydroxy group or carboxyl group, and furthermore, a linear chain having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom , It may contain a branched chain or a cyclic alkyl group.
상기 A성분인 폴리머는, 바람직하게는 상기 식(A)로 표시되는 구조단위를 적어도 2종 갖는 코폴리머, 예를 들어, L이 적어도 1개의 치환기를 가질 수도 있는 2가의 방향족 기를 나타내는 구조단위와, L이 -C(=O)-O-기를 나타내는 구조단위 및/또는 -C(=O)-NH-기를 나타내는 구조단위를 갖는 코폴리머로 할 수 있다.The polymer as the component A is preferably a copolymer having at least two types of structural units represented by the formula (A), for example, a structural unit representing a divalent aromatic group in which L may have at least one substituent, and , L can be a copolymer having a structural unit representing a -C(=O)-O- group and/or a structural unit representing a -C(=O)-NH- group.
또한, 상기 식(A)에 있어서, 상기 L에 있어서의 2가의 방향족 기는 페닐렌기 또는 나프틸렌기로 할 수 있다.In addition, in the formula (A), the divalent aromatic group in L may be a phenylene group or a naphthylene group.
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 상기 A성분인 폴리머는 또한, 하기 식(1-1) 내지 식(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머로 할 수 있다.The polymer which is the component A contained in the coating solution for coating a resist pattern of the present invention can further be a polymer having a structural unit represented by any one of the following formulas (1-1) to (1-4).
[화학식 2][Formula 2]
(식 중, Ar1은 탄소원자수 6 내지 18의 방향족 환을 적어도 1개 포함하는 2가, 4가, 6가 또는 8가의 유기기를 나타내고, Ar2는 메틸렌기 또는 제3급 탄소원자를 개재하여 Ar1과 결합해 있는 탄소원자수 6 내지 18의 방향족 환을 포함하는 2가의 유기기를 나타내고, 상기 방향족 환 중 적어도 1개는 치환기로서 하이드록시기 및/또는 카르복시기를 가진다.)(In the formula, Ar 1 represents a divalent, tetravalent, hexavalent or octavalent organic group containing at least one aromatic ring having 6 to 18 carbon atoms, and Ar 2 is Ar via a methylene group or a tertiary carbon atom. Represents a divalent organic group including an aromatic ring having 6 to 18 carbon atoms bonded to 1, and at least one of the aromatic rings has a hydroxy group and/or a carboxyl group as a substituent.)
상기 식(1-1)~(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머는, 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기를 추가로 함유할 수 있다.A polymer having a structural unit represented by any one of formulas (1-1) to (1-4) is a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. It may contain additionally.
상기 Ar1로 표시되는 2가, 4가, 6가 또는 8가의 유기기는, 예를 들어, 하기 식(2-1) 내지 식(2-5) 중 어느 하나로 표시되는 화합물의 방향족 환상의 임의의 2개소, 4개소, 6개소 또는 8개소로부터의 결합단을 갖는 기이며, 이 결합단과 상기 Ar2로 표시되는 2가의 유기기가 결합하는 것이며, 이 Ar2는 메틸렌기, 하기 식(3-1)로 표시되는 2가의 유기기 또는 하기 식(3-2)로 표시되는 2가의 유기기를 나타내는 것으로 할 수 있다.The divalent, tetravalent, hexavalent or octavalent organic group represented by Ar 1 is, for example, any of the aromatic cyclic compounds represented by any one of the following formulas (2-1) to (2-5) It is a group having a bonding end from 2, 4, 6 or 8 places, and this bonding end and the divalent organic group represented by Ar 2 are bonded, and Ar 2 is a methylene group, the following formula (3-1 ), or a divalent organic group represented by the following formula (3-2).
[화학식 3][Formula 3]
[화학식 4][Formula 4]
〔식 중, R3 내지 R14, R16 및 R17은 각각 독립적으로 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기, 탄소원자수 1 내지 9의 직쇄상 또는 분지쇄상의 알콕시기, 할로겐원자, 니트로기, 시아노기, 아세톡시기, 메틸티오기, 또는 아미노기를 나타내고, 이 알킬기는 적어도 1개의 수소원자가 하이드록시기 또는 할로겐원자로 치환될 수도 있고, 이 아미노기는 적어도 1개의 수소원자가 탄소원자수 1 내지 3의 직쇄상 또는 분지쇄상의 알킬기로 치환될 수도 있고, T3 내지 T14, T16 및 T17은 각각 독립적으로 하이드록시기 또는 카르복시기를 나타내고, T15는 수소원자 또는 메틸기를 나타내고, Q1 및 Q2는 각각 독립적으로 단결합, 산소원자, 황원자, 설포닐기, 카르보닐기, 이미노기, 탄소원자수 6 내지 40의 아릴렌기, 또는 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 혹은 환상의 알킬렌기를 나타내고, 이 알킬렌기는 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있고, m1 내지 m4는 각각 독립적으로 0 내지 2의 정수를 나타내고, r4, r5 및 r8 내지 r14는 각각 독립적으로 0 내지 2의 정수를 나타내고, t4, t5 및 t8 내지 t14는 각각 독립적으로 0 내지 2의 정수를 나타내고, r3, r6, r7 및 r17은 각각 독립적으로 0 내지 8의 정수를 나타내고, t3, t6, t7 및 t17은 각각 독립적으로 0 내지 8의 정수를 나타내고, r16은 0 내지 9의 정수를 나타내고, t16은 0 내지 9의 정수를 나타내고, r3과 t3의 합계, r4와 t4의 합계, r5와 t5의 합계, r6과 t6의 합계, r7과 t7의 합계, r8과 t8의 합계, r9와 t9의 합계, r10과 t10의 합계, r11과 t11의 합계, r12와 t12의 합계, r13과 t13의 합계, r14와 t14의 합계, r16과 t16의 합계, 및 r17과 t17의 합계는 각각 독립적으로 1 내지 10의 정수이다.〕[In the formula, R 3 to R 14 , R 16 and R 17 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, Represents a halogen atom, a nitro group, a cyano group, an acetoxy group, a methylthio group, or an amino group, and in this alkyl group, at least one hydrogen atom may be substituted with a hydroxy group or a halogen atom, and this amino group is at least one hydrogen atom It may be substituted with a linear or branched alkyl group of 1 to 3 embroidery, T 3 to T 14 , T 16 and T 17 each independently represent a hydroxy group or a carboxyl group, and T 15 represents a hydrogen atom or a methyl group , Q 1 and Q 2 are each independently a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, or a straight chain, branched chain or cyclic group having 1 to 10 carbon atoms. Represents an alkylene group, at least one hydrogen atom may be substituted with a halogen atom, m1 to m4 each independently represent an integer of 0 to 2, and r4, r5 and r8 to r14 are each independently 0 to 2 Represents the integer of, t4, t5 and t8 to t14 each independently represent an integer of 0 to 2, r3, r6, r7 and r17 each independently represent an integer of 0 to 8, and t3, t6, t7 and t17 Each independently represents an integer of 0 to 8, r16 represents an integer of 0 to 9, t16 represents an integer of 0 to 9, the sum of r3 and t3, the sum of r4 and t4, the sum of r5 and t5, Sum of r6 and t6, sum of r7 and t7, sum of r8 and t8, sum of r9 and t9, sum of r10 and t10, sum of r11 and t11, sum of r12 and t12, sum of r13 and t13, r14 and The sum of t14, the sum of r16 and t16, and the sum of r17 and t17 are each independently an integer of 1 to 10.]
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 상기 A성분인 폴리머의 중량평균 분자량은, 표준 폴리스티렌 환산으로 1000 이상이다.The weight average molecular weight of the polymer as component A contained in the coating solution for coating a resist pattern of the present invention is 1000 or more in terms of standard polystyrene.
상기 A성분인 폴리머가, 상기 식(A)로 표시되는 구조단위를 갖는 폴리머일 때, 그 중량평균 분자량은 예를 들어 1000 내지 2000이다.When the polymer as the component A is a polymer having a structural unit represented by the formula (A), the weight average molecular weight is, for example, 1000 to 2000.
또한, A성분인 폴리머가, 상기 식(1-1) 내지 식(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머일 때, 그 중량평균 분자량은 예를 들어 1000 내지 20000, 또는 1000 내지 4000이다.In addition, when the polymer as component A is a polymer having a structural unit represented by any one of formulas (1-1) to (1-4), its weight average molecular weight is, for example, 1000 to 20000, or 1000 to It is 4000.
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 상기 B성분인 설폰산은, 그 식 중, A에 있어서의 방향족 기는 예를 들어 페닐기 또는 나프틸기이며, 바람직하게는 페닐기이다.In the sulfonic acid as the component B contained in the coating solution for coating a resist pattern of the present invention, in the formula, the aromatic group in A is, for example, a phenyl group or a naphthyl group, and preferably a phenyl group.
또한 상기 설폰산을 나타내는 식 중, A로 표시되는 기는, 바람직하게는, 탄소원자수 4 내지 12의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 또는 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 페닐기를 나타내고, 그리고 이 설폰산의 함유비율은 상기 A성분인 폴리머에 대하여 0.5질량% 내지 60질량%인 것이 바람직하다.In addition, in the formula representing the sulfonic acid, the group represented by A is preferably a linear or branched alkyl group or fluorinated alkyl group having 4 to 12 carbon atoms, or a phenyl group having at least one alkyl group or fluorinated alkyl group as a substituent. And the content ratio of this sulfonic acid is preferably 0.5% by mass to 60% by mass based on the polymer as the component A.
본 발명의 레지스트 패턴 피복용 도포액은, 1질량ppm 내지 1질량%, 바람직하게는 1질량ppm 내지 0.5질량%의 물을 함유할 수도 있다. 본 발명의 레지스트 패턴 피복용 도포액이 1질량%를 초과하여 물을 함유하는 경우, 이 도포액에 포함되는 유기용매는 물에 쉽게 녹지 않기 때문에, 균일한 용액을 조제하는 것이 곤란해진다. 한편, 본 발명의 레지스트 패턴 피복용 도포액에 포함되는 물의 농도의 하한값은, 수분농도를 측정하기 위하여 일반적으로 사용되는 장치, 예를 들어 칼피셔 수분계의 측정한계값이다. 본 발명의 레지스트 패턴 피복용 도포액에 포함되는 물은, 의도적으로 첨가될 수도 있고, 불순물로서 의도치 않게 포함되는 것일 수도 있다.The coating liquid for coating a resist pattern of the present invention may contain 1 mass ppm to 1 mass%, preferably 1 mass ppm to 0.5 mass% of water. When the coating liquid for coating a resist pattern of the present invention contains water in excess of 1% by mass, since the organic solvent contained in the coating liquid is not easily soluble in water, it becomes difficult to prepare a uniform solution. On the other hand, the lower limit of the concentration of water contained in the coating liquid for coating a resist pattern of the present invention is a measurement limit value of a device generally used for measuring the moisture concentration, for example, a Karl Fischer moisture meter. Water contained in the coating liquid for coating a resist pattern of the present invention may be intentionally added or may be unintentionally included as an impurity.
본 발명의 제2 태양은, 하층막이 형성된 기판 상에 레지스트 패턴을 형성하는 공정, 상기 레지스트 패턴을 피복하도록 본 발명의 레지스트 패턴 피복용 도포액을 도포하는 공정, 상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃ 내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정, 상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정, 및 상기 피복막을 현상액으로 현상후의 레지스트 패턴을, 린스액으로 린스처리하는 공정을 포함하는, 레지스트 패턴의 형성방법이다. 본 발명에 있어서, 린스처리하는 공정이란, 상기 기판 상에 잔류하는 현상액을 린스액으로 치환함으로써, 상기 현상액을 제거하는 공정을 의미한다.The second aspect of the present invention is a step of forming a resist pattern on a substrate on which an underlayer film is formed, a step of applying a coating liquid for coating a resist pattern of the present invention to coat the resist pattern, and applying the coating liquid for coating a resist pattern. A process of forming a coating film on the surface of the resist pattern by heating the substrate at 50°C to 130°C, a process of developing the coating film with a developer after cooling the heated substrate, and a resist pattern after developing the coating film with a developer This is a method of forming a resist pattern including a step of rinsing with a rinse liquid. In the present invention, the step of rinsing refers to a step of removing the developer by replacing the developer remaining on the substrate with a rinsing solution.
본 발명의 제3 태양은, 하층막이 형성된 기판 상에 레지스트 패턴을 형성하는 공정, 상기 레지스트 패턴을 피복하도록 본 발명의 레지스트 패턴 피복용 도포액을 도포하는 공정, 상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃ 내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정, 상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정, 상기 피복막을 현상액으로 현상후의 레지스트 패턴의 패턴간을 충전하도록, 폴리실록산과 물 및/또는 알코올류를 함유하는 용매를 포함하는 제2 도포액을 도포하는 공정, 상기 제2 도포액에 포함되는 폴리실록산 이외의 성분 및 상기 현상액을 제거하거나 또는 감소시켜 도막을 형성하는 공정, 상기 도막을 에치백하여 상기 현상액으로 현상후의 레지스트 패턴의 상면을 노출시키는 공정, 및 상면이 노출된 상기 레지스트 패턴을 제거하는 공정을 포함하는, 반전 패턴의 형성방법이다.A third aspect of the present invention is a step of forming a resist pattern on a substrate on which an underlayer film is formed, a step of applying a coating liquid for coating a resist pattern of the present invention to coat the resist pattern, and applying the coating liquid for coating a resist pattern. Heating the resulting substrate at 50°C to 130°C to form a coating film on the surface of the resist pattern, cooling the heated substrate and then developing the coating film with a developer, and using the coating film with a developer to form a coating film on the surface of the resist pattern. A process of applying a second coating liquid containing a solvent containing polysiloxane and water and/or alcohols to fill between patterns, removing or reducing components other than polysiloxane contained in the second coating liquid and the developer It is a method of forming an inversion pattern, including a step of forming a coating film by etchback, exposing the upper surface of the developed resist pattern with the developer by etching back the coating film, and removing the resist pattern with the upper surface exposed.
본 발명의 반전 패턴의 형성방법에 있어서, 상기 현상액으로 현상하는 공정후, 린스액으로 린스처리하는 공정을 마련할 수도 있다. 즉, 하층막이 형성된 기판 상에 레지스트 패턴을 형성하는 공정, 상기 레지스트 패턴을 피복하도록 본 발명의 레지스트 패턴 피복용 도포액을 도포하는 공정, 상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃ 내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정, 상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정, 상기 피복막을 현상액으로 현상후의 레지스트 패턴을, 린스액으로 린스처리하는 공정, 상기 린스액으로 린스처리후의 레지스트 패턴의 패턴간을 충전하도록, 폴리실록산과 물 및/또는 알코올류를 함유하는 용매를 포함하는 제2 도포액을 도포하는 공정, 상기 제2 도포액에 포함되는 폴리실록산 이외의 성분 및 상기 린스액을 제거하거나 또는 감소시켜 도막을 형성하는 공정, 상기 도막을 에치백하여 상기 린스액으로 린스처리후의 레지스트 패턴의 상면을 노출시키는 공정, 및 상면이 노출된 상기 레지스트 패턴을 제거하는 공정을 포함하는, 반전 패턴의 형성방법이다.In the method of forming a reverse pattern of the present invention, after the step of developing with the developer, a step of rinsing with a rinse liquid may be provided. That is, a process of forming a resist pattern on a substrate on which an underlayer film is formed, a process of applying the coating liquid for coating a resist pattern of the present invention to cover the resist pattern, Heating at 130° C. to form a coating film on the surface of the resist pattern, cooling the heated substrate and developing the coating film with a developer, and rinsing the resist pattern after developing the coating film with a developer and rinse with a rinse solution A step of applying a second coating solution containing a solvent containing polysiloxane and water and/or alcohols so as to fill the pattern of the resist pattern after the rinsing treatment with the rinsing solution, and included in the second coating solution A process of forming a coating film by removing or reducing components other than the polysiloxane and the rinse liquid, a process of etching back the coating film to expose the upper surface of the resist pattern after rinsing with the rinse liquid, and the resist with the upper surface exposed It is a method of forming a reverse pattern, including a step of removing the pattern.
상기 반전 패턴의 형성방법에 있어서, 상기 린스액으로 린스처리하는 공정을 포함하는 경우, 이 린스액이 상기 기판 상에 잔류한 상태로(이 린스액을 제거하지 않고) 상기 제2 도포액을 도포하는 공정을 실시한다. 한편, 린스처리하는 공정을 포함하지 않는 경우, 상기 현상액이 상기 기판 상에 잔류한 상태로(상기 현상액을 제거하지 않고) 상기 제2 도포액을 도포하는 공정을 실시한다.In the case of forming the reverse pattern, when the step of rinsing with the rinse liquid is included, the second coating liquid is applied while the rinse liquid remains on the substrate (without removing the rinse liquid). Perform the process of doing. On the other hand, when the step of rinsing treatment is not included, a step of applying the second coating liquid is performed while the developer remains on the substrate (without removing the developer).
본 발명의 레지스트 패턴 피복용 도포액은, 계면활성제를 필요로 하지 않고, 기판 상에 형성된 라인상 및/또는 필러상의 레지스트 패턴에 균일하게 도포할 수 있다. 본 발명의 레지스트 패턴 피복용 도포액을 이용함으로써, 라인 패턴의 폭과 스페이스 패턴의 폭의 비율이 상이한 라인앤드스페이스 패턴에 있어서도, 라인 패턴의 폭을 균일하게 축소시킬 수 있다. 또한 본 발명의 레지스트 패턴 피복용 도포액은, 함유하는 폴리머를 선택함으로써, 레지스트 패턴의 폭 또는 직경의 축소율을 바꿀 수 있다. 또한, 앞으로 EUV노광이 실용화될 때는, EUV노광을 이용하여 제작한 레지스트 패턴을 추가로 미세화하는 것이 가능해진다.The coating liquid for coating a resist pattern of the present invention does not require a surfactant, and can be uniformly applied to a line-like and/or filler-like resist pattern formed on a substrate. By using the coating liquid for coating a resist pattern of the present invention, even in a line-and-space pattern in which the ratio of the width of the line pattern and the width of the space pattern is different, the width of the line pattern can be uniformly reduced. In addition, the reduction ratio of the width or diameter of the resist pattern can be changed by selecting the polymer contained in the coating liquid for coating a resist pattern of the present invention. Further, when EUV exposure is put into practical use in the future, it becomes possible to further refine the resist pattern produced by using EUV exposure.
도 1은, 실시예 6에 있어서, 실리콘 웨이퍼 상의 축소 레지스트 패턴을 제2 도포액에 의해 매립했을 때의 단면형상을 나타낸 단면SEM상이다.
도 2는, 실시예 7에 있어서, 축소 레지스트 패턴을 제2 도포액에 의해 매립한 후 드라이에칭에 의해 반전 패턴을 형성했을 때의 패턴형상을 나타낸 단면SEM상이다.Fig. 1 is a cross-sectional SEM image showing a cross-sectional shape when a reduced resist pattern on a silicon wafer is embedded with a second coating liquid in Example 6.
Fig. 2 is a cross-sectional SEM image showing a pattern shape when a reversal pattern is formed by dry etching after embedding a reduced resist pattern with a second coating liquid in Example 7.
<A성분: 폴리머><Component A: Polymer>
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 폴리머는, 적어도 1개의 하이드록시기 또는 카르복시기를 함유하는 폴리머이다. 상기 폴리머가 하이드록시기 또는 카르복시기를 함유함으로써, 레지스트 패턴의 표면에 형성되는 피복막의 현상액에 대한 용해성이 발현된다. 또한 상기 폴리머는, 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기를 추가로 함유할 수 있다. 상기 알킬기 중, 예를 들어 tert-부틸기 및 트리플루오로메틸기는, 후술하는 C성분의 유기용매에 대한 상기 폴리머의 용해성의 관점에서 바람직하다.The polymer contained in the coating liquid for coating a resist pattern of the present invention is a polymer containing at least one hydroxy group or carboxyl group. When the polymer contains a hydroxyl group or a carboxyl group, the solubility of the coating film formed on the surface of the resist pattern in the developer solution is expressed. In addition, the polymer may further contain a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. Among the alkyl groups, for example, a tert-butyl group and a trifluoromethyl group are preferable from the viewpoint of the solubility of the polymer in the organic solvent of the component C described later.
[식(A)로 표시되는 구조단위를 갖는 폴리머(폴리머1)][Polymer having a structural unit represented by formula (A) (polymer 1)]
상기 A성분의 폴리머로는, 상기 식(A)로 표시되는 구조단위를 갖는 폴리머(이하, 폴리머1이라 칭함)를 호적하게 이용할 수 있다(단 상기 식(A)로 표시되는 구조단위를 갖는 폴리머는, 적어도 1개의 하이드록시기 또는 카르복시기를 함유하는 것이며, 추가로 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기를 함유할 수 있다).As the polymer of component A, a polymer having a structural unit represented by the formula (A) (hereinafter referred to as polymer 1) may be suitably used (however, a polymer having a structural unit represented by the formula (A)) May contain at least one hydroxy group or carboxyl group, and may further contain a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom).
폴리머1은, 식(A)로 표시되는 구조단위 1종을 단독으로 포함하는 폴리머일 수도 있고, 또한 이 구조단위를 2종 이상 포함하는 폴리머(즉 코폴리머)일 수도 있다.Polymer 1 may be a polymer containing one type of structural unit represented by formula (A) alone, or may be a polymer (ie, a copolymer) containing two or more types of this structural unit.
상기 식(A)에 있어서, X가 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기를 나타내는 경우, 이 알킬기로서, 예를 들어, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, sec-부틸기, tert-부틸기, 헥실기, 옥틸기 및 데실기를 들 수 있고, 이 알킬기의 적어도 1개의 수소원자가 치환되는 할로겐원자로서, 불소, 염소, 브롬 및 요오드를 들 수 있다. 상기 X가 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알콕시기를 나타내는 경우, 이 알콕시기로서, 예를 들어, 메톡시기, 에톡시기, n-프로폭시기, 이소프로폭시기, n-부톡시기, sec-부톡시기, tert-부톡시기, 헥실옥시기, 옥틸옥시기 및 데실옥시기를 들 수 있다.In the above formula (A), when X represents a linear or branched alkyl group having 1 to 10 carbon atoms, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, and n- A butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, an octyl group, and a decyl group, and examples of the halogen atom in which at least one hydrogen atom of the alkyl group is substituted include fluorine, chlorine, bromine and iodine. have. When X represents a linear or branched alkoxy group having 1 to 10 carbon atoms, as this alkoxy group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group , sec-butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, and decyloxy group.
상기 폴리머1이 코폴리머인 경우, 상기 식(A)로 표시되는 적어도 2종의 구조단위는, 랜덤 공중합체, 블록 공중합체, 교호 공중합체 중 어느 하나의 구조를 형성할 수도 있다. 이러한 공중합체로서, 예를 들어, 하기 식(a-1) 내지 식(a-122)에 나타낸 2종 이상의 구조단위를 갖는 공중합체(코폴리머)를 들 수 있다.When the polymer 1 is a copolymer, at least two types of structural units represented by the formula (A) may form any one of a random copolymer, a block copolymer, and an alternating copolymer. As such a copolymer, a copolymer (copolymer) having two or more types of structural units represented by the following formulas (a-1) to (a-122) can be mentioned.
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
상기 식(A)로 표시되는 구조단위를 갖는 폴리머1로는, tert-부틸스티렌 유래의 구조단위, tert-부톡시스티렌 유래의 구조단위, 및 2-비닐나프탈렌 유래의 구조단위로 이루어진 군으로부터 선택되는 적어도 1종의 구조단위와, (메트)아크릴산 유래의 구조단위, (메트)아크릴산하이드록시에틸 유래의 구조단위, 및 (메트)아크릴산하이드록시프로필 유래의 구조단위로 이루어진 군으로부터 선택되는 적어도 1종의 구조단위를 포함하는 폴리머인 것이 바람직하다.Polymer 1 having a structural unit represented by the above formula (A) is selected from the group consisting of a structural unit derived from tert-butylstyrene, a structural unit derived from tert-butoxystyrene, and a structural unit derived from 2-vinylnaphthalene. At least one kind selected from the group consisting of at least one structural unit, a structural unit derived from (meth)acrylic acid, a structural unit derived from hydroxyethyl (meth)acrylate, and a structural unit derived from hydroxypropyl (meth)acrylate It is preferably a polymer containing the structural unit of.
[식(1-1) 내지 식(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머(폴리머2)][Polymer having a structural unit represented by any one of formulas (1-1) to (1-4) (polymer 2)]
상기 A성분의 폴리머로는, 상기 식(1-1) 내지 식(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머(이하, 폴리머2라 칭함)를 호적하게 이용할 수 있다. 상기 식(1-1)~(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머는, 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기를 추가로 함유하는 폴리머로 할 수 있다.As the polymer of the component A, a polymer having a structural unit represented by any one of formulas (1-1) to (1-4) (hereinafter referred to as polymer 2) can be suitably used. A polymer having a structural unit represented by any one of formulas (1-1) to (1-4) is a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. It can be made into a polymer to contain further.
폴리머2는, 상기 식(1-1) 내지 식(1-4)로 표시되는 구조단위 중 어느 1개만을(1종 단독으로) 포함하는 폴리머일 수도 있고, 또한, 식(1-1) 내지 식(1-4)로 표시되는 구조단위 중 어느 1개 또는 2개 이상을 복수종 포함하는 폴리머일 수도 있다.Polymer 2 may be a polymer containing only any one of the structural units represented by formulas (1-1) to (1-4) (one type alone), or formulas (1-1) to It may also be a polymer containing a plurality of types of any one or two or more of the structural units represented by formula (1-4).
폴리머2에 포함되는 상기 식(1-1) 내지 식(1-4)로 표시되는 구조단위 중, 식(1-1)로 표시되는 구조단위가 특히 바람직하다. 또한. 상기 폴리머2가 갖는 구조단위의 종류는, 바람직하게는 2종 내지 5종이며, 더욱 바람직하게는 2종 내지 4종이며, 가장 바람직하게는 2종 또는 3종이다.Among the structural units represented by formulas (1-1) to (1-4) contained in polymer 2, the structural unit represented by formula (1-1) is particularly preferred. Also. The kinds of structural units of the polymer 2 are preferably 2 to 5, more preferably 2 to 4, and most preferably 2 or 3 types.
상기 식(1-1) 내지 식(1-4) 중, Ar1로 표시되는 2가, 4가, 6가 또는 8가의 유기기 또는 Ar2로 표시되는 2가의 유기기에 포함되는 탄소원자수 6 내지 18의 방향족 환은, 예를 들어, 방향족 탄화수소환 또는 복소방향족 환이다. 방향족 탄화수소환으로는, 예를 들어, 벤젠, 나프탈렌, 안트라센, 페난트렌, 나프타센, 트리페닐렌, 피렌 및 크리센을 들 수 있고, 바람직하게는 벤젠, 나프탈렌, 안트라센 및 피렌이다. 복소방향족 환으로는, 예를 들어, 푸란, 티오펜, 피롤, 이미다졸, 피란, 피리딘, 피리미딘, 피라진, 인돌, 푸린, 퀴놀린, 이소퀴놀린, 퀴누클리딘, 크로멘, 티안트렌, 페노티아진, 페녹사진, 크산텐, 아크리딘, 페나진 및 카바졸을 들 수 있고, 바람직하게는 카바졸이다.2 represented by the following, Ar 1 in the formula (1-1) to (1-4), a 4, a carbon source is an organic group including a divalent represented by a 6 or 8-valent organic group, or Ar 2 atoms of 6 to The aromatic ring of 18 is, for example, an aromatic hydrocarbon ring or a heteroaromatic ring. Examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, naphthacene, triphenylene, pyrene and chrysene, and benzene, naphthalene, anthracene and pyrene are preferred. As a heteroaromatic ring, for example, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromane, thianthrene, phenothi Azine, phenoxazine, xanthene, acridine, phenazine, and carbazole, preferably carbazole.
상기 식(2-1) 내지 식(2-5), 식(3-1) 및 식(3-2) 중, R3 내지 R14, R16 및 R17은 각각 독립적으로 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기, 탄소원자수 1 내지 9의 직쇄상 또는 분지쇄상의 알콕시기, 할로겐원자, 니트로기, 시아노기, 아세톡시기, 메틸티오기, 또는 아미노기를 나타낸다. 여기서, 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기로는, 예를 들어, 메틸기, 에틸기, n-프로필기, i-프로필기, 시클로프로필기, n-부틸기, i-부틸기, s-부틸기, t-부틸기, 시클로부틸기, 1-메틸-시클로프로필기, 2-메틸-시클로프로필기, n-펜틸기, 1-메틸-n-부틸기, 2-메틸-n-부틸기, 3-메틸-n-부틸기, 1,1-디메틸-n-프로필기, 1,2-디메틸-n-프로필기, 2,2-디메틸-n-프로필기, 1-에틸-n-프로필기, 시클로펜틸기, 1-메틸-시클로부틸기, 2-메틸-시클로부틸기, 3-메틸-시클로부틸기, 1,2-디메틸-시클로프로필기, 2,3-디메틸-시클로프로필기, 1-에틸-시클로프로필기, 2-에틸-시클로프로필기, n-헥실기, 1-메틸-n-펜틸기, 2-메틸-n-펜틸기, 3-메틸-n-펜틸기, 4-메틸-n-펜틸기, 1,1-디메틸-n-부틸기, 1,2-디메틸-n-부틸기, 1,3-디메틸-n-부틸기, 2,2-디메틸-n-부틸기, 2,3-디메틸-n-부틸기, 3,3-디메틸-n-부틸기, 1-에틸-n-부틸기, 2-에틸-n-부틸기, 1,1,2-트리메틸-n-프로필기, 1,2,2-트리메틸-n-프로필기, 1-에틸-1-메틸-n-프로필기, 1-에틸-2-메틸-n-프로필기, 시클로헥실기, 1-메틸-시클로펜틸기, 2-메틸-시클로펜틸기, 3-메틸-시클로펜틸기, 1-에틸-시클로부틸기, 2-에틸-시클로부틸기, 3-에틸-시클로부틸기, 1,2-디메틸-시클로부틸기, 1,3-디메틸-시클로부틸기, 2,2-디메틸-시클로부틸기, 2,3-디메틸-시클로부틸기, 2,4-디메틸-시클로부틸기, 3,3-디메틸-시클로부틸기, 1-n-프로필-시클로프로필기, 2-n-프로필-시클로프로필기, 1-i-프로필-시클로프로필기, 2-i-프로필-시클로프로필기, 1,2,2-트리메틸-시클로프로필기, 1,2,3-트리메틸-시클로프로필기, 2,2,3-트리메틸-시클로프로필기, 1-에틸-2-메틸-시클로프로필기, 2-에틸-1-메틸-시클로프로필기, 2-에틸-2-메틸-시클로프로필기, 2-에틸-3-메틸-시클로프로필기, 시클로헥실기, 시클로헵틸기, 시클로옥틸기, 시클로노닐기, 시클로데카닐기, 노보닐기, 아다만틸기, 비시클로[2.1.0]펜틸기, 비시클로[3.2.1]옥틸기 및 트리시클로[3.2.1.02,7]옥틸기를 들 수 있다.In formulas (2-1) to (2-5), formulas (3-1), and (3-2), R 3 to R 14 , R 16 and R 17 each independently have 1 to 10 carbon atoms Represents a linear, branched or cyclic alkyl group, a linear or branched alkoxy group having 1 to 9 carbon atoms, a halogen atom, a nitro group, a cyano group, an acetoxy group, a methylthio group, or an amino group. Here, as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl Group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl- n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl -n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl- Cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-phen Tyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl- n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2 -Trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group , 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1 ,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3 ,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1 ,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl -1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, cyclohexyl group, Cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, norbornyl group, adamantyl group, bicyclo[2.1.0]pentyl group, bicyclo[3.2.1]octyl group, and tricyclo[3.2.1.0 2 ,7 ]octyl group.
상기 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기의 적어도 1개의 수소원자는, 할로겐원자로 치환될 수도 있다. 할로겐원자로는, 예를 들어, 불소원자, 염소원자, 브롬원자 및 요오드원자를 들 수 있다. 상기 적어도 1개의 수소원자가 할로겐원자로 치환된 알킬기로서, 바람직하게는, 적어도 1개의 수소원자가 불소원자로 치환된, 메틸기, 에틸기, n-프로필기, i-프로필기, n-부틸기, i-부틸기, s-부틸기 및 t-부틸기이며, 가장 바람직한 것은 트리플루오로메틸기이다.At least one hydrogen atom of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms may be substituted with a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. As an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, preferably, at least one hydrogen atom is substituted with a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group , s-butyl group and t-butyl group, and most preferred is trifluoromethyl group.
상기 탄소원자수 1 내지 9의 직쇄상 또는 분지쇄상의 알콕시기로는, 예를 들어, 메톡시기, 에톡시기, n-프로폭시기, i-프로폭시기, n-부톡시기, i-부톡시기, s-부톡시기, t-부톡시기, n-펜톡시기, 1-메틸-n-부톡시기, 2-메틸-n-부톡시기, 3-메틸-n-부톡시기, 1,1-디메틸-n-프로폭시기, 1,2-디메틸-n-프로폭시기, 2,2-디메틸-n-프로폭시기, 1-에틸-n-프로폭시기, n-헥실옥시기, 1-메틸-n-펜틸옥시기, 2-메틸-n-펜틸옥시기, 3-메틸-n-펜틸옥시기, 4-메틸-n-펜틸옥시기, 1,1-디메틸-n-부톡시기, 1,2-디메틸-n-부톡시기, 1,3-디메틸-n-부톡시기, 2,2-디메틸-n-부톡시기, 2,3-디메틸-n-부톡시기, 3,3-디메틸-n-부톡시기, 1-에틸-n-부톡시기, 2-에틸-n-부톡시기, 1,1,2-트리메틸-n-프로폭시기, 1,2,2,-트리메틸-n-프로폭시기, 1-에틸-1-메틸-n-프로폭시기, 1-에틸-2-메틸-n-프로폭시기, n-헵틸옥시기, n-옥틸옥시기 및 n-노닐옥시기를 들 수 있다.As the linear or branched alkoxy group having 1 to 9 carbon atoms, for example, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s -Butoxy group, t-butoxy group, n-pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-pro Foxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-phen Tyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl- n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1 -Ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2,-trimethyl-n-propoxy group, 1-ethyl- 1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, n-heptyloxy group, n-octyloxy group, and n-nonyloxy group are mentioned.
상기 식(2-1) 내지 식(2-5), 식(3-1) 및 식(3-2) 중, r3 내지 r14, r16 및 r17, 그리고 t3 내지 t14, t16 및 t17은 치환기의 수를 나타내고, m1 내지 m4가 0을 나타내는 경우 벤젠환을 나타내고, 1을 나타내는 경우 나프탈렌환을 나타내고, 3을 나타내는 경우 안트라센환을 나타내고, m1 내지 m4로서 0 또는 1이 바람직하다. 상기 치환기의 수는, Ar1로 표시되는 2가의 유기기 또는 Ar2로 표시되는 2가의 유기기가 포함하는 방향족 환의 종류에 따라, 최대수가 변한다. 상기 치환기의 수는, r3, r6, r7, r16, r17, t3, t6, t7, t16 및 t17은 바람직하게는 1 내지 4의 정수이다. r3과 t3의 합계, r4와 t4의 합계, r5와 t5의 합계, r6과 t6의 합계, r7과 t7의 합계, r8과 t8의 합계, r9와 t9의 합계, r10과 t10의 합계, r11과 t11의 합계, r12와 t12의 합계, r13과 t13의 합계, r14와 t14의 합계, r16과 t16의 합계, 및 r17과 t17의 합계는, 바람직하게는 1 내지 5의 정수이다.In formulas (2-1) to (2-5), (3-1) and (3-2), r3 to r14, r16 and r17, and t3 to t14, t16 and t17 are the number of substituents. Is represented, and when m1 to m4 represents 0, a benzene ring is represented, when 1 is represented, a naphthalene ring is represented, when 3 is represented, an anthracene ring is represented, and 0 or 1 is preferable as m1 to m4. The number of the substituent, according to the type of the aromatic ring include a divalent organic group represented by Ar 2 or a divalent organic group represented by Ar 1, the number of turns up. The number of the substituents r3, r6, r7, r16, r17, t3, t6, t7, t16 and t17 are preferably integers of 1 to 4. sum of r3 and t3, sum of r4 and t4, sum of r5 and t5, sum of r6 and t6, sum of r7 and t7, sum of r8 and t8, sum of r9 and t9, sum of r10 and t10, r11 and The sum of t11, the sum of r12 and t12, the sum of r13 and t13, the sum of r14 and t14, the sum of r16 and t16, and the sum of r17 and t17 are preferably integers of 1 to 5.
상기 식(2-3) 및 식(2-4) 중, Q1 및 Q2는 각각 독립적으로 단결합, 산소원자, 황원자, 설포닐기, 카르보닐기, 이미노기, 탄소원자수 6 내지 40의 아릴렌기, 또는 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 혹은 환상의 알킬렌기를 나타내고, 상기 Q1 및 Q2로서 바람직하게는 단결합이다.In Formulas (2-3) and (2-4), Q 1 and Q 2 are each independently a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, Or a straight-chain, branched-chain or cyclic alkylene group having 1 to 10 carbon atoms, and is preferably a single bond as Q 1 and Q 2 .
상기 탄소원자수 6 내지 40의 아릴렌기로는, 예를 들어, 페닐렌기, o-메틸페닐렌기, m-메틸페닐렌기, p-메틸페닐렌기, o-클로르페닐렌기, m-클로르페닐렌기, p-클로르페닐렌기, o-플루오로페닐렌기, p-플루오로페닐렌기, o-메톡시페닐렌기, p-메톡시페닐렌기, p-니트로페닐렌기, p-시아노페닐렌기, α-나프틸렌기, β-나프틸렌기, o-비페닐리렌기, m-비페닐리렌기, p-비페닐리렌기, 1-안트릴렌기, 2-안트릴렌기, 9-안트릴렌기, 1-페난트릴렌기, 2-페난트릴렌기, 3-페난트릴렌기, 4-페난트릴렌기 및 9-페난트릴렌기를 들 수 있다.Examples of the arylene group having 6 to 40 carbon atoms include phenylene group, o-methylphenylene group, m-methylphenylene group, p-methylphenylene group, o-chlorphenylene group, m-chlorphenylene group, p-chlorphenyl Ene group, o-fluorophenylene group, p-fluorophenylene group, o-methoxyphenylene group, p-methoxyphenylene group, p-nitrophenylene group, p-cyanophenylene group, α-naphthylene group, β -Naphthylene group, o-biphenylylene group, m-biphenylylene group, p-biphenylylene group, 1-anthrylene group, 2-anthrylene group, 9-anthrylene group, 1-phenanthrylene group, 2-phenanthrylene group, 3-phenanthrylene group, 4-phenanthrylene group, and 9-phenanthrylene group are mentioned.
상기 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 혹은 환상의 알킬렌기로는, 예를 들어, 메틸렌기, 에틸렌기, n-프로필렌기, 이소프로필렌기, 시클로프로필렌기, n-부틸렌기, 이소부틸렌기, s-부틸렌기, t-부틸렌기, 시클로부틸렌기, 1-메틸-시클로프로필렌기, 2-메틸-시클로프로필렌기, n-펜틸렌기, 1-메틸-n-부틸렌기, 2-메틸-n-부틸렌기, 3-메틸-n-부틸렌기, 1,1-디메틸-n-프로필렌기, 1,2-디메틸-n-프로필렌기, 2,2-디메틸-n-프로필렌, 1-에틸-n-프로필렌기, 시클로펜틸렌기, 1-메틸-시클로부틸렌기, 2-메틸-시클로부틸렌기, 3-메틸-시클로부틸렌기, 1,2-디메틸-시클로프로필렌기, 2,3-디메틸-시클로프로필렌기, 1-에틸-시클로프로필렌기, 2-에틸-시클로프로필렌기, n-헥실렌기, 1-메틸-n-펜틸렌기, 2-메틸-n-펜틸렌기, 3-메틸-n-펜틸렌기, 4-메틸-n-펜틸렌기, 1,1-디메틸-n-부틸렌기, 1,2-디메틸-n-부틸렌기, 1,3-디메틸-n-부틸렌기, 2,2-디메틸-n-부틸렌기, 2,3-디메틸-n-부틸렌기, 3,3-디메틸-n-부틸렌기, 1-에틸-n-부틸렌기, 2-에틸-n-부틸렌기, 1,1,2-트리메틸-n-프로필렌기, 1,2,2-트리메틸-n-프로필렌기, 1-에틸-1-메틸-n-프로필렌기, 1-에틸-2-메틸-n-프로필렌기, 시클로헥실렌기, 1-메틸-시클로펜틸렌기, 2-메틸-시클로펜틸렌기, 3-메틸-시클로펜틸렌기, 1-에틸-시클로부틸렌기, 2-에틸-시클로부틸렌기, 3-에틸-시클로부틸렌기, 1,2-디메틸-시클로부틸렌기, 1,3-디메틸-시클로부틸렌기, 2,2-디메틸-시클로부틸렌기, 2,3-디메틸-시클로부틸렌기, 2,4-디메틸-시클로부틸렌기, 3,3-디메틸-시클로부틸렌기, 1-n-프로필-시클로프로필렌기, 2-n-프로필-시클로프로필렌기, 1-이소프로필-시클로프로필렌기, 2-이소프로필-시클로프로필렌기, 1,2,2-트리메틸-시클로프로필렌기, 1,2,3-트리메틸-시클로프로필렌기, 2,2,3-트리메틸-시클로프로필렌기, 1-에틸-2-메틸-시클로프로필렌기, 2-에틸-1-메틸-시클로프로필렌기, 2-에틸-2-메틸-시클로프로필렌기, 2-에틸-3-메틸-시클로프로필렌기, n-헵틸렌기, n-옥틸렌기, n-노닐렌기, n-데카닐렌기, 1,2-시클로펜틸렌기, 1,3-시클로펜틸렌기, 1,2-시클로헥실렌기, 1,3-시클로헥실렌기, 1,4-시클로헥실렌기 등을 들 수 있다.Examples of the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutyl Ethylene group, s-butylene group, t-butylene group, cyclobutylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl- n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl- n-propylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclo Propylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentyl Ethylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl- n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2 -Trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene Group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1, 2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,3-trimethyl-cyclopropylene group, 1-ethyl-2-methyl-cyclopropylene group, 2 -Ethyl-1-methyl-cyclopropylene group, 2-ethyl-2-methyl-cyclopropylene group, 2-ethyl-3-methyl-cyclopropylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decanylene group, 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, etc. Can be lifted.
상기 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬렌기의 적어도 1개의 수소원자는, 할로겐원자로 치환될 수도 있다. 할로겐원자로는, 예를 들어, 불소원자, 염소원자, 브롬원자 및 요오드원자를 들 수 있다.At least one hydrogen atom of the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms may be substituted with a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
상기 식(3-1)에 있어서 방향족 환과 결합해 있는 3급 탄소원자, 및 상기 식(3-2)에 있어서 방향족 환과 결합해 있는 2개의 메틸렌기는, 각각 상기 Ar1로 표시되는 2가, 4가, 6가 또는 8가의 유기기와의 결합에 관련된 부분이다.The tertiary carbon atom bonded to the aromatic ring in the formula (3-1) and the two methylene groups bonded to the aromatic ring in the formula (3-2) are divalent and 4, respectively, represented by Ar 1 It is a moiety related to bonding with an a, hexavalent or octavalent organic group.
상기 폴리머2는, 상기 Ar1로 표시되는 2가, 4가, 6가 또는 8가의 유기기를 구성하기 위한 모노머와 상기 Ar2로 표시되는 2가의 유기기를 구성하기 위한 모노머의 반응에 의해 호적하게 얻어진다.The polymer 2 is 2 represented by the above Ar 1, 4 a, obtained suitably by the monomer the reaction for forming a divalent organic group represented by the monomers and the Ar 2 for constituting an organic group 6 or 8-valent Lose.
상기 Ar1로 표시되는 2가, 4가, 6가 또는 8가의 유기기를 구성하기 위한 모노머의 구체예로는, 이하에 나타낸 (식 3-1-1) 내지 (식 3-1-26), (식 4-1-1) 내지 (식 4-1-10), (식 4-13) 내지 (식 4-39) 및 (식 5-1) 내지 (식 5-19)로 표시되는 화합물을 들 수 있다.Specific examples of the monomer for constituting the divalent, tetravalent, hexavalent or octavalent organic group represented by Ar 1 include (Formula 3-1-1) to (Formula 3-1-26) shown below, Compounds represented by (Formula 4-1-1) to (Formula 4-1-10), (Formula 4-13) to (Formula 4-39) and (Formula 5-1) to (Formula 5-19) Can be lifted.
[화학식 16][Formula 16]
[화학식 17][Formula 17]
[화학식 18][Formula 18]
[화학식 19][Formula 19]
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
[화학식 23][Formula 23]
상기 Ar2로 표시되는 2가의 유기기를 구성하기 위한 모노머의 구체예로는, 이하에 나타낸, 알데히드기를 갖는 (식 6-1) 내지 (식 6-37)로 표시되는 화합물, 메틸올기를 갖는 (식 7-1) 내지 (식 7-15)로 표시되는 화합물을 들 수 있다.As a specific example of the monomer for constituting the divalent organic group represented by Ar 2 , a compound represented by (Formula 6-1) to (Formula 6-37) having an aldehyde group, and a methylol group ( The compounds represented by Formula 7-1) to (Formula 7-15) can be mentioned.
[화학식 24][Formula 24]
[화학식 25][Formula 25]
[화학식 26][Formula 26]
[화학식 27][Formula 27]
[화학식 28][Formula 28]
그 중에서도, 상기 Ar1로 표시되는 2가의 유기기를 구성하기 위한 모노머가 페놀성 하이드록시기를 갖는 모노머이며, 상기 Ar2로 표시되는 2가의 유기기를 구성하기 위한 모노머가 알데히드기를 갖는 모노머인 것이 바람직하다.Among them, it is preferable that the monomer constituting the divalent organic group represented by Ar 1 is a monomer having a phenolic hydroxy group, and the monomer constituting the divalent organic group represented by Ar 2 is a monomer having an aldehyde group. .
상기 폴리머2에 포함되는 상기 식(1-1) 내지 식(1-4) 중 어느 하나로 표시되는 구조단위의 구체예로는, 예를 들어, 이하에 나타낸 (식 10-1) 내지 (식 10-36)으로 표시되는 구조단위를 들 수 있으나, 이들로 한정되지 않는다.Specific examples of the structural unit represented by any one of the formulas (1-1) to (1-4) contained in the polymer 2 include, for example, (Formula 10-1) to (Formula 10) shown below. The structural unit represented by -36) may be mentioned, but is not limited thereto.
[화학식 29][Chemical Formula 29]
[화학식 30][Formula 30]
[화학식 31][Formula 31]
[화학식 32][Formula 32]
[화학식 33][Formula 33]
[화학식 34][Formula 34]
[화학식 35][Formula 35]
[화학식 36][Formula 36]
[화학식 37][Formula 37]
[화학식 38][Formula 38]
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 상기 폴리머2의 합성방법으로는, 상기 Ar1를 구성하는 모노머군인 「모노머A군」과, 상기 Ar2를 구성하는 모노머군인 「모노머B군」을 산촉매하에서 축합중합하는 것이 일반적이다. 모노머A군 또는 모노머B군은 각각 1종 또는 2종 이상이나, 바람직하게는 각각 3종 이내, 보다 바람직하게는 각각 2종 이내이다. 또한, 폴리머2 합성시에 있어서의, 모노머A군의, 모노머B군에 대한 투입몰비(모노머A군/모노머B군)는, 예를 들어 20/100 내지 80/20, 보다 바람직하게는 20/80 내지 70/30으로 할 수 있다.In the method for synthesizing the polymer 2 contained in the coating solution for coating a resist pattern of the present invention, the "monomer group A" as a monomer group constituting Ar 1 and the "monomer group B" as a monomer group constituting the Ar 2 It is common to perform condensation polymerization under an acid catalyst. Each of the monomer A group or the monomer B group is 1 type or 2 or more types, preferably 3 types or less, and more preferably 2 types or less, respectively. In addition, the input molar ratio of the monomer A group to the monomer B group (monomer A group/monomer B group) in the synthesis of polymer 2 is, for example, 20/100 to 80/20, more preferably 20/ It can be 80 to 70/30.
또한, 이 모노머A군 또는 모노머B군 중에 적어도 1개의 수소원자가 불소원자로 치환된 알킬기 또는 알킬렌기를 포함하는 모노머가 포함되는 것이 바람직하다.Further, it is preferable that a monomer containing an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a fluorine atom is contained in the monomer A group or the monomer B group.
모노머A군 또는 모노머B군이 2종 이상인 모노머로 이루어진 경우, 이 모노머A군 또는 모노머B군 중에 포함되는, 적어도 1개의 수소원자가 불소원자로 치환된 알킬기 또는 알킬렌기를 포함하는 모노머의 투입몰비는, 예를 들어 1/10 내지 1이며, 보다 바람직하게는 1/5 내지 1이다.When the monomer A group or the monomer B group consists of two or more kinds of monomers, the input molar ratio of the monomers containing an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a fluorine atom included in the monomer A group or the monomer B group is, For example, it is 1/10 to 1, More preferably, it is 1/5 to 1.
나아가, 모노머A군 또는 모노머B군이 2종 이상인 모노머로 이루어진 경우, 모노머A군 전체 또는 모노머B군 전체에 대하여, 2종 이상으로 이루어진 모노머의 각 모노머의 투입몰비는, 1/20 이상이며, 보다 바람직하게는 1/10 이상으로 할 수 있다.Further, when the monomer A group or the monomer B group consists of two or more kinds of monomers, the input molar ratio of each monomer of the two or more kinds of monomers to the entire monomer A group or the entire monomer B group is 1/20 or more, More preferably, it can be 1/10 or more.
상기 모노머A군과 모노머B군의 반응은, 질소분위기하에서 행해지는 것이 바람직하다. 반응온도는 50℃ 내지 200℃, 바람직하게는 80℃ 내지 180℃의 임의의 온도를 선택할 수 있고, 1시간 내지 48시간의 반응시간으로 고분자량의 중합체를 얻을 수 있다. 저분자량으로 보존안정성이 높은 중합체를 얻으려면, 80℃ 내지 150℃의 반응온도에서 1시간 내지 24시간의 반응시간이 보다 바람직하다.It is preferable that the reaction between the monomer A group and the monomer B group is carried out in a nitrogen atmosphere. The reaction temperature can be selected from 50°C to 200°C, preferably from 80°C to 180°C, and a high molecular weight polymer can be obtained with a reaction time of 1 hour to 48 hours. In order to obtain a polymer having high storage stability with a low molecular weight, a reaction time of 1 hour to 24 hours at a reaction temperature of 80°C to 150°C is more preferable.
<B성분: 설폰산><B component: sulfonic acid>
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 설폰산은, A-SO3H(식 중, A는 탄소원자수 1 내지 16의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 방향족기, 또는 메틸기, 에틸기와 같은 치환기를 가질 수도 있는 탄소원자수 4 내지 16의 지환식 기를 나타낸다.)로 표시되는 화합물이다. 이러한 설폰산으로서, 예를 들어, 옥틸벤젠설폰산, 노닐벤젠설폰산, 데실벤젠설폰산, 운데실벤젠설폰산, 도데실벤젠설폰산(별명: 라우릴벤젠설폰산), (1,3,5,7-테트라메틸옥틸)벤젠설폰산, 트리데실벤젠설폰산, (1R)-(-)-10-캠퍼설폰산, (1S)-(+)-10-캠퍼설폰산, 트리플루오로메탄설폰산, 퍼플루오로부탄설폰산, 퍼플루오로옥탄설폰산, 노나플루오로-1-부탄설폰산을 들 수 있다.The sulfonic acid contained in the coating solution for coating a resist pattern of the present invention is A-SO 3 H (wherein A is a linear or branched alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms, and this alkyl group or fluorinated alkyl group is a substituent. As at least one aromatic group or an alicyclic group having 4 to 16 carbon atoms which may have a substituent such as a methyl group or an ethyl group. As such sulfonic acid, for example, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid (alias: laurylbenzenesulfonic acid), (1,3, 5,7-tetramethyloctyl)benzenesulfonic acid, tridecylbenzenesulfonic acid, (1R)-(-)-10-camphorsulfonic acid, (1S)-(+)-10-camphorsulfonic acid, trifluoromethane Sulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, and nonafluoro-1-butanesulfonic acid.
이들 설폰산 중, 본 발명의 레지스트 패턴 피복용 도포액에 포함되는 성분으로서, 상기 설폰산을 나타내는 식 중, A로 표시되는 기가, 탄소원자수 4 내지 12의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 또는 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 페닐기를 나타내는 설폰산이 바람직하고, 도데실벤젠설폰산 및 노나플루오로-1-부탄설폰산이 바람직하게 이용된다.Among these sulfonic acids, as a component contained in the coating solution for coating a resist pattern of the present invention, in the formula representing the sulfonic acid, the group represented by A is a linear or branched alkyl group or fluorinated alkyl group having 4 to 12 carbon atoms. Or a sulfonic acid representing a phenyl group having at least one substituent of this alkyl group or a fluorinated alkyl group as a substituent is preferable, and dodecylbenzenesulfonic acid and nonafluoro-1-butanesulfonic acid are preferably used.
상기 설폰산의 함유비율은, 상기 (A)성분의 폴리머에 대하여, 예를 들어 0.5질량% 내지 80질량%, 바람직하게는 0.5질량% 내지 60질량%, 또는 20질량% 내지 60질량%이다.The content ratio of the sulfonic acid is, for example, 0.5% by mass to 80% by mass, preferably 0.5% by mass to 60% by mass, or 20% by mass to 60% by mass with respect to the polymer of the component (A).
<C성분: 유기용매><C component: organic solvent>
본 발명의 레지스트 패턴 피복용 도포액에 포함되는 유기용매는, R1-O-R2 및/또는 R1-C(=O)-R2(식 중, R1은 탄소원자수 3 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타내고, R2는 탄소원자수 1 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타낸다.)로 표시되는 화합물로 이루어지고, 상기 A성분의 폴리머(폴리머1, 폴리머2)를 용해 가능한 것이 필요하다. 이러한 유기용매로서, 예를 들어, 이소프로필에테르(별명: 디이소프로필에테르), 프로필에테르(별명: 디프로필에테르), 이소아밀에테르(별명: 디이소아밀에테르), 아밀에테르(별명: 디아밀에테르), 디부틸에테르(별명: 부틸에테르), 디이소부틸에테르(별명: 이소부틸에테르), sec-부틸에테르(별명: 디-sec-부틸에테르), 헥실에테르(별명: 디헥실에테르), 비스(2-에틸헥실)에테르, 데실에테르(별명: 디데실에테르), 운데실에테르(별명: 디운데실에테르), 도데실에테르(별명: 디도데실에테르), 테트라데실에테르(별명: 디테트라데실에테르), 헥사데실에테르, 부틸메틸에테르, 부틸에틸에테르, 부틸프로필에테르, tert-부틸메틸에테르, tert-부틸에틸에테르, tert-부틸프로필에테르, 디-tert-부틸에테르, 시클로펜틸메틸에테르, 시클로헥실메틸에테르, 시클로펜틸에틸에테르, 시클로헥실에틸에테르, 시클로펜틸프로필에테르, 시클로펜틸-2-프로필에테르, 시클로헥실프로필에테르, 시클로헥실-2-프로필에테르, 시클로펜틸부틸에테르, 시클로펜틸-tert-부틸에테르, 시클로헥실부틸에테르, 시클로헥실-tert-부틸에테르, 2-옥타논 및 4-헵타논을 들 수 있다. 이들 유기용매 중, 본 발명의 레지스트 패턴 피복용 도포액에 포함되는 성분으로서, 이소아밀에테르 및 2-옥타논이 바람직하게 이용된다.The organic solvent contained in the coating solution for coating a resist pattern of the present invention is R 1 -OR 2 and/or R 1 -C(=O)-R 2 (wherein R 1 is a straight chain having 3 to 16 carbon atoms. , A branched or cyclic alkyl group or a fluorinated alkyl group, and R 2 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms.) It is necessary that the polymer (polymer 1, polymer 2) can be dissolved. As such an organic solvent, for example, isopropyl ether (alias: diisopropyl ether), propyl ether (alias: dipropyl ether), isoamyl ether (alias: diisoamyl ether), amyl ether (alias: diamyl Ether), dibutyl ether (alias: butyl ether), diisobutyl ether (alias: isobutyl ether), sec-butyl ether (alias: di-sec-butyl ether), hexyl ether (alias: dihexyl ether), Bis(2-ethylhexyl) ether, decyl ether (alias: didecyl ether), undecyl ether (alias: diundecyl ether), dodecyl ether (alias didodecyl ether), tetradecyl ether (alias: ditetra Decyl ether), hexadecyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-butyl propyl ether, di-tert-butyl ether, cyclopentyl methyl ether, Cyclohexylmethyl ether, cyclopentylethyl ether, cyclohexylethyl ether, cyclopentylpropyl ether, cyclopentyl-2-propyl ether, cyclohexylpropyl ether, cyclohexyl-2-propyl ether, cyclopentylbutyl ether, cyclopentyl-tert -Butyl ether, cyclohexylbutyl ether, cyclohexyl-tert-butyl ether, 2-octanone, and 4-heptanone. Among these organic solvents, isoamyl ether and 2-octanone are preferably used as components contained in the coating liquid for coating a resist pattern of the present invention.
본 발명의 레지스트 패턴 피복용 도포액으로부터, 상기 유기용매 및 임의로 함유하는 물을 제거한 고형분의 함유비율은, 이 도포액에 대하여, 예를 들어 0.5질량% 내지 30질량%, 바람직하게는 2질량% 내지 15질량%이다.In the coating solution for coating a resist pattern of the present invention, the content ratio of the solid content obtained by removing the organic solvent and water optionally contained is, for example, 0.5% by mass to 30% by mass, preferably 2% by mass with respect to this coating solution. To 15% by mass.
[레지스트 패턴의 형성방법][Method of forming resist pattern]
본 발명은, 상기 레지스트 패턴 피복액을 이용한 레지스트 패턴의 형성방법도 그 대상으로 한다.The present invention also provides a method for forming a resist pattern using the resist pattern coating liquid.
본 발명의 레지스트 패턴의 형성방법은, 하층막이 형성된 기판 상에 레지스트 패턴을 형성하는 공정, 상기 레지스트 패턴을 피복하도록 본 발명의 레지스트 패턴 피복용 도포액을 도포하는 공정, 상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃ 내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정, 상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정, 및 상기 피복막을 현상액으로 현상후의 레지스트 패턴을, 린스액으로 린스처리하는 공정을 포함하고, 이 방법에 의해, 기판 상에 당초 형성된 레지스트 패턴보다 미세화(축소화)된 레지스트 패턴을 형성할 수 있다.The method of forming a resist pattern of the present invention includes a step of forming a resist pattern on a substrate on which an underlayer film is formed, a step of applying a coating liquid for coating a resist pattern of the present invention to coat the resist pattern, and a coating liquid for coating the resist pattern. After heating the coated substrate at 50°C to 130°C to form a coating film on the surface of the resist pattern, cooling the heated substrate, developing the coating film with a developer, and developing the coating film with a developer. It includes a step of rinsing the resist pattern with a rinsing liquid, and by this method, a resist pattern that is finer (reduced) than the resist pattern originally formed on the substrate can be formed.
여기서, 상기 기판으로서, 정밀집적회로소자의 제조에 사용되는 기판(예를 들어, 산화규소막, 질화규소막 또는 산화질화규소막으로 피복된 실리콘기판 등의 반도체기판, 질화규소기판, 석영기판, 무알칼리 유리기판, 저알칼리 유리기판, 결정화 유리기판, ITO막이 형성된 유리기판)을 들 수 있다. 그리고, 상기 기판에는, 하층막으로서, 반사방지능을 갖는 유기막 및/또는 무기막이 형성되어 있다.Here, as the substrate, a substrate used for manufacturing a precision integrated circuit device (for example, a semiconductor substrate such as a silicon oxide film, a silicon nitride film or a silicon substrate coated with a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, an alkali-free glass A substrate, a low-alkali glass substrate, a crystallized glass substrate, and a glass substrate on which an ITO film is formed). Further, on the substrate, an organic film and/or an inorganic film having antireflection ability are formed as an underlayer film.
상기 레지스트 패턴의 형상으로서, 예를 들어, 라인상 및 필러상(기둥상)을 들 수 있고, 고립라인 패턴, 라인앤드스페이스 패턴, 고립도트 패턴, 밀집도트 패턴 중 어느 하나를 형성할 수도 있다. 라인상의 레지스트 패턴의 형상은 직선으로 한정되지 않고 절곡된 형상일 수도 있고, 상기 필러상의 레지스트 패턴의 형상은, 기둥상이면 각기둥 및 원기둥 어느 것일 수도 있다. 이러한 형상의 레지스트 패턴은, 공지의 포지티브형 레지스트용액(예를 들어, 스미토모화학(주)제 PAR710, PAR855, 및 JSR(주)제 AR2772JN)을 이용하고, 공지의 리소그래피프로세스에 의해 형성할 수 있다. 사용하는 노광장치의 광원으로서, 예를 들어, i선, KrF 엑시머레이저, ArF 엑시머레이저 및 EUV를 채용할 수 있다.As the shape of the resist pattern, for example, a line shape and a pillar shape (column shape) may be exemplified, and any one of an isolated line pattern, a line and space pattern, an isolated dot pattern, and a dense dot pattern may be formed. The shape of the line-shaped resist pattern is not limited to a straight line and may be a bent shape, and the shape of the pillar-shaped resist pattern may be either a prism or a cylinder if it is a columnar shape. A resist pattern of such a shape can be formed by a known lithography process using a known positive resist solution (e.g., Sumitomo Chemical Co., Ltd. PAR710, PAR855, and JSR Co., Ltd. AR2772JN). . As the light source of the exposure apparatus to be used, for example, i-line, KrF excimer laser, ArF excimer laser and EUV can be employed.
본 발명의 레지스트 패턴 피복용 도포액을 도포하는 공정에 있어서, 이 도포액은, 스피너, 코터 등의 적당한 도포방법에 의해, 상기 레지스트 패턴을 형성후의 기판 상에 도포된다.In the step of applying the coating liquid for coating a resist pattern of the present invention, the coating liquid is applied onto the substrate after formation of the resist pattern by an appropriate coating method such as a spinner or a coater.
상기 레지스트 패턴 피복용 도포액이 도포된 기판을 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정에 있어서, 기판을 가열하는 공정은, 본 발명의 레지스트 패턴 피복용 도포액에 포함되는 설폰산을, 상기 레지스트 패턴의 표면에 확산시키기 위하여 행해진다. 따라서, 상기 가열온도는, 설폰산이 확산되기에 필요한 온도이면 되고, 단, 레지스트 패턴의 형상을 현저히 변형(예를 들어 멜트플로우)시키지 않는 온도여야 한다. 따라서, 상기 가열온도는, 130℃보다 낮은 온도, 예를 들어 100℃를 초과하지 않는 온도가 보다 바람직하다. 또한 상기 가열온도에 있어서의 가열에 의해서는, 본 발명의 레지스트 패턴 피복용 도포액은 경화되지 않는다.In the step of forming a coating film on the surface of the resist pattern by heating a substrate to which the resist pattern coating liquid is applied, the step of heating the substrate comprises: sulfonic acid contained in the resist pattern coating liquid of the present invention. , To diffuse on the surface of the resist pattern. Accordingly, the heating temperature may be a temperature necessary for diffusion of sulfonic acid, provided that the shape of the resist pattern is not significantly changed (eg, melt flow). Therefore, the heating temperature is more preferably a temperature lower than 130°C, for example, a temperature not exceeding 100°C. Further, by heating at the above heating temperature, the coating liquid for coating a resist pattern of the present invention is not cured.
상기 가열·피복막의 형성공정후, 상기 피복막을 현상하는 공정에서 이용하는 상기 현상액으로서, 예를 들어, 수산화나트륨, 수산화칼륨, 탄산나트륨, 규산나트륨, 메타규산나트륨, 암모니아수 등의 무기알칼리류, 에틸아민, n-프로필아민 등의 제1 아민류, 디에틸아민, 디-n-부틸아민 등의 제2 아민류, 트리에틸아민, 메틸디에틸아민 등의 제3 아민류, 디메틸에탄올아민, 트리에탄올아민 등의 알코올아민류, 테트라메틸암모늄하이드록시드, 테트라에틸암모늄하이드록시드, 콜린 등의 제4급 암모늄염, 피롤, 피페리딘 등의 환상 아민류, 등의 알칼리류의 수용액을 들 수 있다. 나아가, 상기 알칼리류의 수용액에 이소프로필알코올 등의 알코올류, 비이온계 등의 계면활성제를 적당량 첨가하여 사용할 수도 있다. 이들 중에서 바람직한 현상액은 제4급 암모늄염의 수용액, 더욱 바람직하게는 테트라메틸암모늄하이드록시드의 수용액이다.As the developer used in the process of developing the coating film after the heating/coating film formation process, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, First amines such as n-propylamine, second amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine , Tetramethylammonium hydroxide, tetraethylammonium hydroxide, and quaternary ammonium salts such as choline, cyclic amines such as pyrrole and piperidine, and an aqueous solution of alkalis such as. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic type may be added to the aqueous solution of the alkali. Among these, a preferred developer is an aqueous solution of a quaternary ammonium salt, more preferably an aqueous solution of tetramethylammonium hydroxide.
또한 상기 현상공정후, 린스처리하는 공정에서 이용하는 상기 린스액으로서, 예를 들어, 순수, 및 계면활성제의 수용액을 들 수 있다.In addition, as the rinse liquid used in the rinse treatment step after the development step, for example, pure water and an aqueous solution of a surfactant may be mentioned.
[반전 패턴의 형성방법][Method of forming inversion pattern]
본 발명은, 상기 레지스트 패턴 피복액을 이용한 반전 패턴의 형성방법도 그 대상으로 한다.Another object of the present invention is a method of forming a reverse pattern using the resist pattern coating solution.
본 발명의 반전 패턴의 형성방법은, 레지스트 패턴을 형성하는 공정, 레지스트 패턴 피복용 도포액을 도포하는 공정, 이 도포액이 도포된 기판을 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정, 이 가열후에 상기 피복막을 현상액으로 현상하는 공정까지, 혹은 나아가, 린스액으로 린스처리하는 공정까지는, 상기 [레지스트 패턴의 형성방법]에 있어서의 각 공정에 따라 실시하고, 그 후, 레지스트 패턴의 패턴간을 충전하도록, 폴리실록산과 물 및/또는 알코올류를 함유하는 용매를 포함하는 제2 도포액을 도포하는 공정, 상기 제2 도포액에 포함되는 폴리실록산 이외의 성분 및 상기 현상액 혹은 상기 린스액을 제거하거나 또는 감소시켜 도막을 형성하는 공정, 상기 도막을 에치백하여 상기 현상액으로 현상후 또는 린스액으로 린스처리후의 레지스트 패턴의 상면을 노출시키는 공정, 및 상면이 노출된 상기 레지스트 패턴을 제거하는 공정을 포함하고, 반전 패턴이 형성된다.The method of forming a reverse pattern of the present invention includes a step of forming a resist pattern, a step of applying a coating liquid for coating a resist pattern, a step of heating a substrate to which the coating liquid is applied to form a coating film on the surface of the resist pattern, After this heating, up to the step of developing the coating film with a developer, or further, up to the step of rinsing with a rinse liquid, is carried out according to each step in the above [Resist Pattern Formation Method], and thereafter, the pattern of the resist pattern A step of applying a second coating liquid containing a solvent containing polysiloxane and water and/or alcohols to fill the liver, removing components other than polysiloxane contained in the second coating liquid, and the developer or the rinse solution A process of forming a coating film by performing or decreasing, etching back the coating film to expose the upper surface of the resist pattern after development with the developer or after rinsing with a rinse solution, and a process of removing the resist pattern with the upper surface exposed. And a reverse pattern is formed.
여기서, 상기 제2 도포액에 포함되는 폴리실록산은, 특별히 한정되지 않으나, 예를 들어, 하기 식(11)로 표시되는 화합물 및 하기 식(12)로 표시되는 화합물의 공가수분해 축합물에 하기 식(13)으로 표시되는 화합물을 혼합하고, 얻어진 생성물을 들 수 있다.Here, the polysiloxane contained in the second coating liquid is not particularly limited, but, for example, the following formula in the cohydrolysis condensate of the compound represented by the following formula (11) and the compound represented by the following formula (12) The product obtained by mixing the compound represented by (13) is mentioned.
[화학식 39][Formula 39]
(식 중, R18은 탄소원자수 1 내지 12의 유기기를 나타내고, Y 및 Z는 각각 독립적으로 메틸기 또는 에틸기를 나타내고, R19 및 R20은 각각 독립적으로 직쇄상 또는 분지쇄상의 탄소원자수 1 내지 3의 알킬렌기를 나타내고, R21은 탄소원자수 1 내지 4의 알콕시기, 알릴옥시기 또는 하이드록시기를 나타내고, p는 0, 1 또는 2를 나타낸다.)(In the formula, R 18 represents an organic group having 1 to 12 carbon atoms, Y and Z each independently represent a methyl group or an ethyl group, and R 19 and R 20 each independently represent a linear or branched carbon atom number of 1 to 3 Represents an alkylene group of, R 21 represents an alkoxy group having 1 to 4 carbon atoms, an allyloxy group or a hydroxy group, and p represents 0, 1 or 2.)
또한, 상기 제2 도포액에 포함되는 알코올류는, 예를 들어, 상기 식(13)으로 표시되는 화합물이며, 이 식(13)으로 표시되는 화합물로서, 예를 들어, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노프로필에테르, 프로필렌글리콜모노부틸에테르, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노알릴에테르, 디프로필렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노부틸에테르, 트리에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노에틸에테르, 트리에틸렌글리콜모노프로필에테르, 트리에틸렌글리콜모노부틸에테르, 에틸렌글리콜, 1,2-프로판디올 또는 1,3-프로판디올, 디에틸렌글리콜, 디프로필렌글리콜, 디이소프로필렌글리콜 및 트리에틸렌글리콜을 들 수 있다.In addition, alcohols contained in the second coating liquid are, for example, a compound represented by the formula (13), and as a compound represented by this formula (13), for example, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoallyl ether, dipropylene Glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, ethylene glycol, 1,2-propanediol or 1,3-propanediol, diethylene glycol, dipropylene glycol, diisopropylene glycol, and triethylene glycol.
상기 서술한 도막을 형성하는 공정에 있어서, 상기 제2 도포액에 포함되는 폴리실록산 이외의 성분 및 상기 현상액(혹은 린스액)을 제거하거나 또는 감소시킨다는 것은, 예를 들어, 상기 제2 도포액이 도포된 상기 하층막이 형성된 기판을, 스핀드라이하거나, 또는 스핀드라이후 가열함으로써 실시된다. 여기서, 스핀드라이란, 기판을 회전시키면서 건조시키는 것이다. 또한, 상기 제2 도포액에 포함되는 폴리실록산 이외의 성분이란, 물 및/또는 알코올류를 함유하는 용매, 및 필요에 따라 첨가되는 첨가제이다.In the process of forming the above-described coating film, removing or reducing components other than polysiloxane contained in the second coating solution and the developer (or rinse solution) means, for example, applying the second coating solution. The substrate on which the lower layer film is formed is spin-dried or heated after spin-drying. Here, spin-drying means drying the substrate while rotating it. In addition, a component other than polysiloxane contained in the said 2nd coating liquid is a solvent containing water and/or alcohol, and an additive added as needed.
상기 레지스트 패턴의 상면을 노출되는 공정에 있어서 행하는 상기 도막에 대한 에치백은, 예를 들어, CF4 등의 불소계 가스를 이용하는 드라이에칭, 유기산 혹은 유기염기의 수용액을 이용한 웨트에칭, 유기용제를 이용한 웨트에칭, 또는 CMP법에 의해 행해지고, 처리조건은 적당히 조정가능하다.Etch-back to the coating film performed in the step of exposing the upper surface of the resist pattern is, for example, dry etching using a fluorine-based gas such as CF 4 , wet etching using an aqueous solution of an organic acid or organic base, or using an organic solvent. It is carried out by wet etching or the CMP method, and the treatment conditions can be appropriately adjusted.
상기 상면이 노출된 상기 레지스트 패턴을 제거하는 공정은, 예를 들어, O2와 N2의 혼합가스 혹은 O2가스를 이용한 드라이에칭, 또는 애싱에 의해 행해진다. 애싱에 의해 행해지는 경우, 상기 레지스트 패턴만이 선택적으로 제거되는 조건으로 실시할 필요가 있다.The step of removing the resist pattern from which the upper surface is exposed is performed, for example, by dry etching using a mixed gas of O 2 and N 2 or an O 2 gas, or ashing. When it is performed by ashing, it is necessary to perform it under the condition that only the resist pattern is selectively removed.
[실시예][Example]
본 명세서의 하기 합성예 1 내지 합성예 4에서 얻어지는 폴리머, 합성예 5에서 얻어지는 공가수분해 축합물, 그리고 합성예 6 내지 합성예 8에서 얻어지는 폴리머의 중량평균 분자량(Mw)은, 겔퍼미에이션 크로마토그래피(Gel Permeation Chromatography, 이하 GPC라 약칭함)에 의한 측정결과이다. 측정에는 토소주식회사제 GPC장치를 이용하고, 측정조건은 하기와 같다.The weight average molecular weight (Mw) of the polymers obtained in Synthesis Examples 1 to 4 below, the cohydrolyzed condensates obtained in Synthesis Example 5, and the polymers obtained in Synthesis Examples 6 to 8 are determined by gel permeation chromatography. This is a measurement result by graphing (Gel Permeation Chromatography, hereinafter abbreviated as GPC). For the measurement, a GPC apparatus manufactured by Tosoh Corporation was used, and the measurement conditions are as follows.
측정장치: HLC-8020GPC〔상품명〕(토소(주)제)Measuring device: HLC-8020GPC [brand name] (manufactured by Tosoh Corporation)
GPC칼럼: TSKgel〔등록상표〕 G2000HXL; 2개, TSKgel G3000HXL; 1개, 및 TSKgel G4000HXL; 1개(이상, 토소(주)제)GPC column: TSKgel [registered trademark] G2000HXL; 2, TSKgel G3000HXL; 1, and TSKgel G4000HXL; 1 (or more, manufactured by Tosoh Corporation)
칼럼온도: 40℃Column temperature: 40°C
용매: 테트라하이드로푸란(THF)Solvent: tetrahydrofuran (THF)
유량: 1.0mL/분Flow: 1.0 mL/min
표준시료: 폴리스티렌(토소(주)제)Standard sample: Polystyrene (manufactured by Tosoh Corporation)
<합성예 1><Synthesis Example 1>
tert-부틸스티렌 11.0g(도쿄카세이공업(주)제), 메타크릴산 4.0g(도쿄카세이공업(주)제) 및 아조비스이소부티로니트릴 1.71g(도쿄카세이공업(주)제)을 유산에틸 43.0g에 용해시켰다. 그 용액을 가열환류한 유산에틸 100.4g에 천천히 적하하고, 적하후, 160℃에서 가열환류하여 24시간 반응시켜, 폴리머를 함유하는 용액을 얻었다. 이 반응용액을 물/메탄올 혼합용매 2,000g에 침전시켜, 얻어진 백색고체를 여과후, 60℃에서 하룻밤 감압건조하고, 백색의 폴리머를 얻었다. 이 폴리머에 대하여 GPC분석을 행한 결과, 표준 폴리스티렌 환산으로 중량평균 분자량 1,965였다. 얻어진 폴리머는 하기 식으로 표시되는 구조단위를 갖는 코폴리머(공중합체)인 것으로 추정된다.11.0 g of tert-butyl styrene (manufactured by Tokyo Kasei Industries, Ltd.), 4.0 g of methacrylic acid (manufactured by Tokyo Kasei Industries, Ltd.) and 1.71 g of azobisisobutyronitrile (manufactured by Tokyo Kasei Industries, Ltd.) It was dissolved in 43.0 g of ethyl. The solution was slowly added dropwise to 100.4 g of heated refluxed ethyl lactate, and after the dropwise addition, the solution was heated to reflux at 160° C. and reacted for 24 hours to obtain a polymer-containing solution. The reaction solution was precipitated in 2,000 g of a water/methanol mixed solvent, and the obtained white solid was filtered and dried under reduced pressure at 60° C. overnight to obtain a white polymer. As a result of GPC analysis of this polymer, the weight average molecular weight was 1,965 in terms of standard polystyrene. It is estimated that the obtained polymer is a copolymer (copolymer) having a structural unit represented by the following formula.
[화학식 40][Formula 40]
<합성예 2><Synthesis Example 2>
tert-부틸스티렌 9.5g(도쿄카세이공업(주)제), 메타크릴산 4.1g(도쿄카세이공업(주)제), N-이소프로필아크릴아미드 1.3g(도쿄카세이공업(주)제) 및 아조비스이소부티로니트릴 0.98g(도쿄카세이공업(주)제)을 유산에틸 43.1g에 용해시켰다. 그 용액을 가열환류한 유산에틸 100.7g에 천천히 적하하고, 적하후, 160℃에서 가열환류하여 24시간 반응시켜, 폴리머를 함유하는 용액을 얻었다. 이 반응용액을 물/메탄올 혼합용매 2,000g에 침전시켜, 얻어진 백색고체를 여과후, 60℃에서 하룻밤 감압건조하고, 백색의 폴리머를 얻었다. 이 폴리머에 대하여 GPC분석을 행한 결과, 표준 폴리스티렌 환산으로 중량평균 분자량 1,809였다. 얻어진 폴리머는 하기 식으로 표시되는 구조단위를 갖는 코폴리머(공중합체)인 것으로 추정된다.9.5 g of tert-butyl styrene (manufactured by Tokyo Kasei Industries, Ltd.), 4.1 g of methacrylic acid (manufactured by Tokyo Kasei Industries, Ltd.), 1.3 g of N-isopropylacrylamide (manufactured by Tokyo Kasei Industries, Ltd.) and azo 0.98 g of bisisobutyronitrile (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 43.1 g of ethyl lactate. The solution was slowly added dropwise to 100.7 g of heated refluxed ethyl lactate, and after the dropwise addition, the solution was heated to reflux at 160° C. and reacted for 24 hours to obtain a solution containing a polymer. The reaction solution was precipitated in 2,000 g of a water/methanol mixed solvent, and the obtained white solid was filtered and dried under reduced pressure at 60° C. overnight to obtain a white polymer. As a result of performing GPC analysis on this polymer, the weight average molecular weight was 1,809 in terms of standard polystyrene. It is estimated that the obtained polymer is a copolymer (copolymer) having a structural unit represented by the following formula.
[화학식 41][Formula 41]
<합성예 3><Synthesis Example 3>
tert-부틸스티렌 9.1g(도쿄카세이공업(주)제), 메타크릴산 3.9g(도쿄카세이공업(주)제), 메타크릴산2,2,2-트리플루오로에틸메타크릴레이트 1.9g(도쿄카세이공업(주)제) 및 아조비스이소부티로니트릴 1.71g(도쿄카세이공업(주)제)을 유산에틸 43.0g에 용해시켰다. 그 용액을 가열환류한 유산에틸 100.4g에 천천히 적하하고, 적하후, 160℃에서 가열환류하여 24시간 반응시켜, 폴리머를 함유하는 용액을 얻었다. 이 반응용액을 물/메탄올 혼합용매 2,000g에 침전시켜, 얻어진 백색고체를 여과후, 60℃에서 하룻밤 감압건조하고, 백색의 폴리머를 얻었다. 이 폴리머에 대하여 GPC분석을 행한 결과, 표준 폴리스티렌 환산으로 중량평균 분자량 1,550이었다. 얻어진 폴리머는 하기 식으로 표시되는 구조단위를 갖는 코폴리머(공중합체)인 것으로 추정된다.9.1 g of tert-butyl styrene (manufactured by Tokyo Kasei Industries, Ltd.), 3.9 g of methacrylic acid (manufactured by Tokyo Kasei Industries, Ltd.), 1.9 g of methacrylic acid 2,2,2-trifluoroethyl methacrylate ( Tokyo Kasei Industrial Co., Ltd. product) and azobisisobutyronitrile 1.71 g (Tokyo Kasei Industrial Co., Ltd. product) were dissolved in 43.0 g of ethyl lactate. The solution was slowly added dropwise to 100.4 g of heated refluxed ethyl lactate, and after the dropwise addition, the solution was heated to reflux at 160° C. and reacted for 24 hours to obtain a polymer-containing solution. The reaction solution was precipitated in 2,000 g of a water/methanol mixed solvent, and the obtained white solid was filtered and dried under reduced pressure at 60° C. overnight to obtain a white polymer. As a result of performing GPC analysis on this polymer, the weight average molecular weight was 1,550 in terms of standard polystyrene. It is estimated that the obtained polymer is a copolymer (copolymer) having a structural unit represented by the following formula.
[화학식 42][Formula 42]
<합성예 4><Synthesis Example 4>
tert-부틸스티렌 8.7g(도쿄카세이공업(주)제), 메타크릴산 3.7g(도쿄카세이공업(주)제) 및 메타크릴산1,1,1,3,3,3-헥사플루오로이소프로필 2.6g(도쿄카세이공업(주)제) 및 아조비스이소부티로니트릴 0.98g(도쿄카세이공업(주)제)을 유산에틸 43.1g에 용해시켰다. 그 용액을 가열환류한 유산에틸 100.11g에 천천히 적하하고, 적하후, 160℃에서 가열환류하여 24시간 반응시켜, 폴리머를 함유하는 용액을 얻었다. 이 반응용액을 물/메탄올 혼합용매 2,000g에 침전시켜, 얻어진 백색고체를 여과후, 60℃에서 하룻밤 감압건조하고, 백색의 폴리머를 얻었다. 이 폴리머에 대하여 GPC분석을 행한 결과, 표준 폴리스티렌 환산으로 중량평균 분자량 1,847이었다. 얻어진 폴리머는 하기 식으로 표시되는 구조단위를 갖는 코폴리머(공중합체)인 것으로 추정된다.8.7 g of tert-butyl styrene (manufactured by Tokyo Kasei Industries, Ltd.), 3.7 g of methacrylic acid (manufactured by Tokyo Kasei Industries, Ltd.) and methacrylic acid 1,1,1,3,3,3-hexafluoroiso 2.6 g of propyl (manufactured by Tokyo Kasei Industries, Ltd.) and 0.98 g of azobisisobutyronitrile (manufactured by Tokyo Kasei Industries, Ltd.) were dissolved in 43.1 g of ethyl lactate. The solution was slowly added dropwise to 100.11 g of heated-refluxed ethyl lactate, and after the dropwise addition, the solution was heated to reflux at 160° C. and reacted for 24 hours to obtain a solution containing a polymer. The reaction solution was precipitated in 2,000 g of a water/methanol mixed solvent, and the obtained white solid was filtered and dried under reduced pressure at 60° C. overnight to obtain a white polymer. As a result of performing GPC analysis on this polymer, the weight average molecular weight was 1,847 in terms of standard polystyrene. It is estimated that the obtained polymer is a copolymer (copolymer) having a structural unit represented by the following formula.
[화학식 43][Formula 43]
<합성예 5><Synthesis Example 5>
테트라에톡시실란 5.8g(30mol%), 메틸트리에톡시실란 6.7g(40mol%), 하기 식으로 표시되는 화합물인 5-(트리에톡시실릴)노보난-2,3-디카르본산무수물 9.2g(30mol%), 아세톤 43g 및 초순수 43g을 200ml의 플라스크에 넣고, 그 플라스크내의 혼합용액을 마그네틱스터러로 교반하면서 0.01mol/L의 염산 1.7g을 그 혼합용액에 적하하였다. 적하후, 40℃로 조정된 오일배스에 플라스크를 옮기고, 가온환류하에서 240분 반응시켰다. 그 후, 반응용액을 실온까지 냉각하고, 그 반응용액에 프로필렌글리콜모노메틸에테르 24.0g을 첨가하고, 아세톤, 물 및 염산, 그리고 반응부생물인 에탄올을 반응용액으로부터 감압유거하여 농축해서, 공가수분해 축합물(폴리실록산)의 프로필렌글리콜모노메틸에테르용액을 얻었다. 고형분농도는 140℃에 있어서의 고형잔물 환산으로 15질량%가 되도록 조정하였다. GPC에 의한 중량평균 분자량은 표준 폴리스티렌 환산으로 1,000이었다.Tetraethoxysilane 5.8 g (30 mol%), methyltriethoxysilane 6.7 g (40 mol%), 5-(triethoxysilyl) nobonane-2,3-dicarboxylic acid anhydride 9.2, a compound represented by the following formula g (30 mol%), 43 g of acetone and 43 g of ultrapure water were put into a 200 ml flask, and 1.7 g of 0.01 mol/L hydrochloric acid was added dropwise to the mixed solution while stirring the mixed solution in the flask with a magnetic stirrer. After dropping, the flask was transferred to an oil bath adjusted to 40°C, and reacted for 240 minutes under heated reflux. After that, the reaction solution was cooled to room temperature, 24.0 g of propylene glycol monomethyl ether was added to the reaction solution, and acetone, water and hydrochloric acid, and ethanol as a reaction by-product were distilled off under reduced pressure from the reaction solution and concentrated. A propylene glycol monomethyl ether solution of the decomposed condensate (polysiloxane) was obtained. The solid content concentration was adjusted to be 15% by mass in terms of solid residue at 140°C. The weight average molecular weight by GPC was 1,000 in terms of standard polystyrene.
[화학식 44][Formula 44]
<합성예 6><Synthesis Example 6>
트리스(4-하이드록시페닐)에탄(도쿄카세이공업(주)제) 45.00g, 3,5-비스(트리플루오로메틸)벤즈알데히드(도쿄카세이공업(주)제) 53.35g 및 메탄설폰산(도쿄카세이공업(주)제) 2.12g에, 프로필렌글리콜모노메틸에테르 150.70g을 첨가하고, 질소분위기하, 6시간 환류교반하였다. 반응종료 후, 반응액을 수중에 적하하여 재침전시켰다. 얻어진 침전물을 여과, 세정하고, 60℃에서 감압건조함으로써, 폴리머 66.06g을 얻었다. 이 폴리머의, GPC에 의해 표준 폴리스티렌 환산으로 측정되는 중량평균 분자량은 2100이었다. 얻어진 폴리머는, 하기 식으로 표시되는 구조단위를 갖는 노볼락 수지인 것으로 추정된다.Tris(4-hydroxyphenyl)ethane (manufactured by Tokyo Kasei Industries, Ltd.) 45.00 g, 3,5-bis (trifluoromethyl) benzaldehyde (manufactured by Tokyo Kasei Industries, Ltd.) 53.35 g and methanesulfonic acid (manufactured by Tokyo Kasei Industries, Ltd.) To 2.12 g of Kasei Industrial Co., Ltd.), 150.70 g of propylene glycol monomethyl ether was added, and the mixture was stirred under reflux for 6 hours in a nitrogen atmosphere. After completion of the reaction, the reaction solution was dripped into water to reprecipitate. The obtained precipitate was filtered, washed, and dried under reduced pressure at 60°C to obtain 66.06 g of a polymer. The weight average molecular weight of this polymer measured in terms of standard polystyrene by GPC was 2100. It is estimated that the obtained polymer is a novolac resin having a structural unit represented by the following formula.
[화학식 45][Formula 45]
<합성예 7><Synthesis Example 7>
플로로글루시놀(도쿄카세이공업(주)제) 50.00g, 3,4-디하이드록시벤즈알데히드(도쿄카세이공업(주)제) 16.43g, 3,5-비스(트리플루오로메틸)벤즈알데히드(도쿄카세이공업(주)제) 67.20g 및 메탄설폰산(도쿄카세이공업(주)제) 3.81g에, 프로필렌글리콜모노메틸에테르 206.15g을 첨가하고, 질소분위기하, 4시간 환류교반하였다. 반응종료 후, 반응액을 수중에 적하하여 재침전시켰다. 얻어진 침전물을 여과, 세정하고, 60℃에서 감압건조함으로써, 폴리머 102.83g을 얻었다. 이 폴리머의, GPC로부터 표준 폴리스티렌 환산으로 측정되는 중량평균 분자량은 2400이었다. 얻어진 폴리머는, 하기 식으로 표시되는 2종의 구조단위를 갖는 노볼락 수지인 것으로 추정된다.Phloroglucinol (manufactured by Tokyo Kasei Industries, Ltd.) 50.00 g, 3,4-dihydroxybenzaldehyde (manufactured by Tokyo Kasei Industries, Ltd.) 16.43 g, 3,5-bis (trifluoromethyl) benzaldehyde (Tokyo To 67.20 g of Kasei Industries, Ltd.) and 3.81 g of methanesulfonic acid (manufactured by Tokyo Kasei Industries, Ltd.) were added 206.15 g of propylene glycol monomethyl ether, followed by reflux stirring in a nitrogen atmosphere for 4 hours. After completion of the reaction, the reaction solution was dripped into water to reprecipitate. The obtained precipitate was filtered, washed, and dried under reduced pressure at 60°C to obtain 102.83 g of a polymer. The weight average molecular weight of this polymer measured by GPC in terms of standard polystyrene was 2400. The obtained polymer is estimated to be a novolac resin having two types of structural units represented by the following formula.
[화학식 46][Chemical Formula 46]
<합성예 8><Synthesis Example 8>
트리스(4-하이드록시페닐)에탄(도쿄카세이공업(주)제) 40.00g, 3,4-디하이드록시벤즈알데히드(도쿄카세이공업(주)제) 3.61g, 3,5-비스(트리플루오로메틸)벤즈알데히드(도쿄카세이공업(주)제) 56.90g 및 메탄설폰산(도쿄카세이공업(주)제) 2.51g에, 프로필렌글리콜모노메틸에테르 154.53g을 첨가하고, 질소분위기하, 6시간 환류교반하였다. 반응종료 후, 반응액을 수중에 적하하여 재침전시켰다. 얻어진 침전물을 여과, 세정하고, 60℃에서 감압건조함으로써, 폴리머 63.01g을 얻었다. 이 폴리머의, GPC로부터 표준 폴리스티렌 환산으로 측정되는 중량평균 분자량은 2600이었다. 얻어진 폴리머는, 하기 식으로 표시되는 2종의 구조단위를 갖는 노볼락 수지인 것으로 추정된다.Tris(4-hydroxyphenyl)ethane (manufactured by Tokyo Kasei Industries, Ltd.) 40.00g, 3,4-dihydroxybenzaldehyde (manufactured by Tokyo Kasei Industries, Ltd.) 3.61g, 3,5-bis (trifluoro) To 56.90 g of methyl) benzaldehyde (manufactured by Tokyo Kasei Industries, Ltd.) and 2.51 g of methanesulfonic acid (manufactured by Tokyo Kasei Industries, Ltd.), 154.53 g of propylene glycol monomethyl ether was added, followed by reflux stirring for 6 hours under a nitrogen atmosphere. I did. After completion of the reaction, the reaction solution was dripped into water to reprecipitate. The obtained precipitate was filtered, washed, and dried under reduced pressure at 60°C to obtain 63.01 g of a polymer. The weight average molecular weight of this polymer measured by GPC in terms of standard polystyrene was 2600. The obtained polymer is estimated to be a novolac resin having two types of structural units represented by the following formula.
[화학식 47][Chemical Formula 47]
<실시예 1><Example 1>
상기 합성예 1에서 얻어진 폴리머 1.33g에 도데실벤젠설폰산(준세이화학(주)제) 0.67g 및 이소아밀에테르 18.0g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.33 g of the polymer obtained in Synthesis Example 1, 0.67 g of dodecylbenzenesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) and 18.0 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<실시예 2><Example 2>
상기 합성예 2에서 얻어진 폴리머 1.33g에 도데실벤젠설폰산(준세이화학(주)제) 0.67g 및 이소아밀에테르 18.0g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.33 g of the polymer obtained in Synthesis Example 2, 0.67 g of dodecylbenzenesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) and 18.0 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<실시예 3><Example 3>
상기 합성예 3에서 얻어진 폴리머 1.33g에 도데실벤젠설폰산(준세이화학(주)제) 0.67g 및 이소아밀에테르 18.0g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.33 g of the polymer obtained in Synthesis Example 3, 0.67 g of dodecylbenzenesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) and 18.0 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<실시예 4><Example 4>
상기 합성예 4에서 얻어진 폴리머 1.00g에 도데실벤젠설폰산(준세이화학(주)제) 0.50g 및 이소아밀에테르 13.50g을 첨가하여 용해하였다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.00 g of the polymer obtained in Synthesis Example 4, 0.50 g of dodecylbenzenesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) and 13.50 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<비교예 1><Comparative Example 1>
상기 합성예 4에서 얻어진 폴리머 1.5g에 이소아밀에테르 13.5g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.13.5 g of isoamyl ether was added to 1.5 g of the polymer obtained in Synthesis Example 4 and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<실시예 8><Example 8>
상기 합성예 6에서 얻어진 폴리머 1.0g에 도데실벤젠설폰산(준세이화학(주)제) 0.50g 및 이소아밀에테르 13.5g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.0 g of the polymer obtained in Synthesis Example 6, 0.50 g of dodecylbenzenesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) and 13.5 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<실시예 9><Example 9>
상기 합성예 7에서 얻어진 폴리머 1.0g에 도데실벤젠설폰산(준세이화학(주)제) 0.50g 및 이소아밀에테르 13.5g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.0 g of the polymer obtained in Synthesis Example 7, 0.50 g of dodecylbenzenesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) and 13.5 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<실시예 10><Example 10>
상기 합성예 8에서 얻어진 폴리머 1.0g에 도데실벤젠설폰산(준세이화학(주)(제)) 0.50g 및 이소아밀에테르 13.5g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.To 1.0 g of the polymer obtained in Synthesis Example 8, 0.50 g of dodecylbenzenesulfonic acid (Junsei Chemical Co., Ltd. (manufactured)) and 13.5 g of isoamyl ether were added and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
<비교예 2><Comparative Example 2>
상기 합성예 8에서 얻어진 폴리머 1.5g에 이소아밀에테르 13.5g을 첨가하여 용해시켰다. 그 후 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 패턴 피복용 도포액을 조제하였다.13.5 g of isoamyl ether was added to 1.5 g of the polymer obtained in Synthesis Example 8 and dissolved. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to prepare a coating liquid for coating a resist pattern.
〔포지티브형 레지스트 프로세스에 대한 적용시험〕[Application test for positive resist process]
본 발명의 실시예 1 내지 실시예 4, 실시예 8 내지 실시예 10, 및 비교예 1 및 비교예 2에서 조제한 레지스트 패턴 피복용 도포액을, 스피너를 이용하여 실리콘 웨이퍼 상에 도포하고, 핫플레이트 상에서, 75℃에서 1분간 가열한 도막의 막두께 측정을 행하였다(막두께 A: 도막의 막두께). 상기 도막상에 시판의 알칼리성 현상액(도쿄오카공업(주)제, 제품명: NMD-3)을 퍼들하여 60초 방치하고, 3000rpm으로 회전시키면서 30초간 순수로 린스를 행하였다. 린스후, 100℃에서 60초간 베이크하고, 막두께 측정을 행하였다(막두께 B). 그 결과를 표 1(표 1-1 및 표 1-2)에 나타낸다. 막두께 B가 0nm인 경우, 현상액에 의해 도막은 제거되었다고 할 수 있다. 이는, 본 발명의 레지스트 패턴 피복용 도포액이, 포지티브형 레지스트 프로세스에 적용가능한 것을 나타낸다.The coating liquid for coating a resist pattern prepared in Examples 1 to 4, 8 to 10, and Comparative Examples 1 and 2 of the present invention was applied onto a silicon wafer using a spinner, and a hot plate On the top, the film thickness of the coating film heated at 75°C for 1 minute was measured (film thickness A: film thickness of the coating film). A commercially available alkaline developer (manufactured by Tokyo Oka Industrial Co., Ltd., product name: NMD-3) was puddled on the coating film and allowed to stand for 60 seconds, and rinsed with pure water for 30 seconds while rotating at 3000 rpm. After rinsing, it was baked at 100°C for 60 seconds, and the film thickness was measured (film thickness B). The results are shown in Table 1 (Tables 1-1 and 1-2). When the film thickness B is 0 nm, it can be said that the coating film has been removed by the developer. This shows that the coating liquid for coating a resist pattern of the present invention is applicable to a positive resist process.
[표 1][Table 1]
〔포토레지스트 패턴의 형성〕[Formation of photoresist pattern]
ARC29A(닛산화학공업(주)제)를 스피너에 의해 실리콘 웨이퍼 상에 도포하였다. 그 실리콘 웨이퍼를 핫플레이트 상에 배치하고, 205℃에서 1분간 가열하여, 막두께 80nm의 레지스트 하층막을 형성하였다. 이 레지스트 하층막 상에, 시판의 포토레지스트용액(스미토모화학(주)제, 상품명: PAR855)을 스피너에 의해 도포하고, 핫플레이트 상에서 105℃에서 60초간 가열하여 포토레지스트막(막두께 0.10μm)을 형성하였다.ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer with a spinner. The silicon wafer was placed on a hot plate and heated at 205° C. for 1 minute to form a resist underlayer film having a thickness of 80 nm. On this resist underlayer film, a commercially available photoresist solution (manufactured by Sumitomo Chemical Co., Ltd., trade name: PAR855) was applied with a spinner, and heated on a hot plate at 105°C for 60 seconds to obtain a photoresist film (film thickness of 0.10 μm). Formed.
이어서, 스캐너((주)니콘제, NSR-S307E(파장 193nm, NA: 0.85, σ: 0.65/0.93))를 이용하고, 포토마스크를 통과하여 노광을 행하였다. 포토마스크는 형성해야 하는 레지스트 패턴에 따라 선택된다. 노광후, 핫플레이트상, 105℃에서 60초간 노광후 가열(PEB)을 행하고, 냉각후, 공업규격의 60초 싱글패들식 공정에서, 현상액으로서 0.26규정의 테트라메틸암모늄하이드록시드 수용액을 이용하여 현상하였다. 이상의 공정을 거쳐, 목적으로 하는 레지스트 패턴을 형성하였다. 형성된 라인앤드스페이스 패턴에 대하여, 라인 패턴의 폭을 측정하였다.Next, using a scanner (manufactured by Nikon Corporation, NSR-S307E (wavelength: 193 nm, NA: 0.85, σ: 0.65/0.93)), exposure was performed through a photomask. The photomask is selected according to the resist pattern to be formed. After exposure, on a hot plate, heat (PEB) after exposure at 105°C for 60 seconds, and after cooling, in an industrial standard 60 second single paddle process, a 0.26 standard tetramethylammonium hydroxide aqueous solution is used as a developer. And developed. Through the above steps, a target resist pattern was formed. With respect to the formed line and space pattern, the width of the line pattern was measured.
〔레지스트 패턴 축소프로세스〕[Resist pattern reduction process]
실리콘 웨이퍼 상에 형성된 레지스트 패턴(1:1의 라인앤드스페이스 패턴) 상에, 본 발명의 실시예 1 내지 실시예 4, 실시예 8 내지 실시예 10, 및 비교예 1 및 비교예 2에서 조제한 레지스트 패턴 피복용 도포액을, 스피너를 이용하여 각각 도포하고, 75℃에서 베이크후, 현상액으로서 0.26규정의 테트라메틸암모늄하이드록시드 수용액을 이용하여 현상하였다. 현상후의 라인앤드스페이스 패턴에 대하여, 라인 패턴의 폭을 측정하였다. 그 결과를 표 2(표 2-1 및 표 2-2)에 나타낸다.On the resist pattern (1:1 line-and-space pattern) formed on a silicon wafer, the resists prepared in Examples 1 to 4, 8 to 10, and Comparative Examples 1 and 2 of the present invention The coating liquids for pattern coating were each applied using a spinner, baked at 75° C., and developed using a 0.26 standard tetramethylammonium hydroxide aqueous solution as a developer. For the line and space pattern after development, the width of the line pattern was measured. The results are shown in Table 2 (Table 2-1 and Table 2-2).
[표 2][Table 2]
이어서, 실리콘 웨이퍼 상에 형성한 4종의 레지스트 패턴(고립라인 패턴, 1:3, 1:2 및 1:1.25의 라인앤드스페이스 패턴) 상에, 본 발명의 실시예 4 또는 실시예 10에서 조제한 레지스트 패턴 피복용 도포액을, 스피너를 이용하여 각각 도포하고, 75℃에서 베이크후, 현상액으로서 0.26규정의 테트라메틸암모늄하이드록시드 수용액을 이용하여 현상하였다. 현상후의 고립라인 패턴 및 라인앤드스페이스 패턴에 대하여, 라인 패턴의 폭을 측정하였다. 그 결과를 표 3에 나타낸다.Subsequently, on 4 types of resist patterns (isolated line patterns, 1:3, 1:2 and 1:1.25 line-and-space patterns) formed on a silicon wafer, prepared in Example 4 or Example 10 of the present invention The resist pattern coating liquid was applied using a spinner, baked at 75 DEG C, and developed using a 0.26 standard tetramethylammonium hydroxide aqueous solution as a developer. With respect to the isolated line pattern and the line and space pattern after development, the width of the line pattern was measured. The results are shown in Table 3.
[표 3][Table 3]
<실시예 5><Example 5>
〔레지스트 패턴 축소 프로세스〕[Resist pattern reduction process]
실리콘 웨이퍼 상에 형성된 레지스트 패턴(1:1의 라인앤드스페이스 패턴) 상에, 본 발명의 실시예 1에서 조제한 레지스트 패턴 피복용 도포액을, 스피너를 이용하여 도포하고, 85℃에서 베이크후, 현상액으로서 0.26규정의 테트라메틸암모늄하이드록시드 수용액을 이용하여 현상하고, 라인 패턴의 폭이 축소된 레지스트 패턴(이하, 본 명세서에서는 축소 레지스트 패턴이라 칭함)을 얻었다. 얻어진 축소 레지스트 패턴의 형상을 단면SEM에 의해 관찰하였다.On the resist pattern (1:1 line-and-space pattern) formed on the silicon wafer, the coating solution for coating the resist pattern prepared in Example 1 of the present invention was applied using a spinner, and after baking at 85°C, a developer As a result, a resist pattern with a reduced width of the line pattern (hereinafter referred to as a reduced resist pattern) was obtained by developing using an aqueous solution of 0.26 specified tetramethylammonium hydroxide. The shape of the resulting reduced resist pattern was observed by cross-section SEM.
<실시예 6><Example 6>
〔축소 레지스트 패턴의 매립프로세스〕[Reduction resist pattern embedding process]
실리콘 웨이퍼 상에 형성된 레지스트 패턴(1:1의 라인앤드스페이스 패턴) 상에, 본 발명의 실시예 1에서 조제한 레지스트 패턴 피복용 도포액을, 스피너를 이용하여 도포하고, 85℃에서 베이크후, 현상액으로서 0.26규정의 테트라메틸암모늄하이드록시드 수용액을 이용하여 현상하고, 축소 레지스트 패턴을 얻었다. 계속해서, 이 실리콘 웨이퍼 상에, 상기 합성예 5에서 얻어진 폴리실록산용액에 초순수 및 프로필렌글리콜모노메틸에테르를 각각 7대3(질량비)의 비율로 첨가하여 조제한 제2 도포액을 도포하고, 0.26규정의 테트라메틸암모늄 수용액을 이 제2 도포액에 치환하였다. 그 후, 상기 실리콘 웨이퍼를 1500rpm으로 60초간 스핀하여 도포액 중의 용제를 건조시킨 후, 100℃에서 60초간 가열하여 도막을 형성하고, 상기 축소 레지스트 패턴의 매립을 행하였다. 매립후의 모습을 단면SEM에 의해 관찰하였다. 그 결과를 도 1에 나타낸다.On the resist pattern (1:1 line-and-space pattern) formed on the silicon wafer, the coating solution for coating the resist pattern prepared in Example 1 of the present invention was applied using a spinner, and after baking at 85°C, a developer As a result, it was developed using a 0.26 standard tetramethylammonium hydroxide aqueous solution to obtain a reduced resist pattern. Subsequently, on the silicon wafer, a second coating solution prepared by adding ultrapure water and propylene glycol monomethyl ether in a ratio of 7 to 3 (mass ratio) to the polysiloxane solution obtained in Synthesis Example 5 was applied, and 0.26 An aqueous solution of tetramethylammonium was substituted for this second coating solution. Thereafter, the silicon wafer was spun at 1500 rpm for 60 seconds to dry the solvent in the coating solution, and then heated at 100° C. for 60 seconds to form a coating film, and the reduced resist pattern was embedded. The state after embedding was observed by cross-section SEM. The results are shown in FIG. 1.
<실시예 7><Example 7>
〔반전 패턴의 형성프로세스〕〔Process of forming inversion pattern〕
상기 제2 도포액을 이용하여 형성한 도막을, CF4(유량 50sccm)와 Ar(유량200sccm)의 혼합가스를 이용한 드라이에칭에 의해 에치백하고, 레지스트 패턴의 상부를 노출시켰다. 그 후, O2(유량 10sccm)와 N2(유량 20sccm)의 혼합가스를 이용한 드라이에칭에 의해 상기 레지스트 패턴을 제거하고, 반전 패턴을 얻었다. 반전 패턴의 형상을 단면SEM에 의해 관찰하였다. 그 결과를 도 2에 나타낸다.The coating film formed using the second coating solution was etched back by dry etching using a mixed gas of CF 4 (flow rate 50 sccm) and Ar (flow rate 200 sccm), and the upper portion of the resist pattern was exposed. Thereafter, the resist pattern was removed by dry etching using a mixed gas of O 2 (flow rate 10 sccm) and N 2 (flow rate 20 sccm) to obtain an inversion pattern. The shape of the inversion pattern was observed by cross-sectional SEM. The results are shown in FIG. 2.
하기 표 4에, 패턴의 매립성 및 패턴 형상의 평가결과를 정리하였다. 표 4에 있어서, 「양호」란, 패턴 매립성에 관해서는 보이드(공동)가 발생하는 일 없이 레지스트 패턴을 매립한 것을 나타내고, 패턴 형상에 관해서는 패턴 무너짐, 및 스컴(scum)이 발생하는 일 없이 패턴이 형성된 것을 나타낸다.In Table 4 below, the evaluation results of the embedding property and pattern shape of the pattern are summarized. In Table 4, ``good'' indicates that the resist pattern is embedded without causing voids (cavities) in the pattern embedding property, and in terms of the pattern shape, pattern collapse and scum do not occur. It indicates that the pattern has been formed.
[표 4][Table 4]
Claims (15)
B성분: A-SO3H(식 중, A는 탄소원자수 1 내지 16의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 방향족기, 또는 치환기를 가질 수도 있는 탄소원자수 4 내지 16의 지환식 기를 나타낸다.)로 표시되는 설폰산, 그리고
C성분: R1-O-R2 및 R1-C(=O)-R2 중 적어도 하나(식 중, R1은 탄소원자수 3 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타내고, R2는 탄소원자수 1 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타낸다.)로 표시되는 화합물로 이루어진, 상기 폴리머를 용해가능한 유기용매,
를 포함하는 레지스트 패턴 피복용 도포액으로서,
상기 A성분인 폴리머가, 하기 식(A)로 표시되는 구조단위를 적어도 2종 갖는 코폴리머이며,
(식 중, R0은 수소원자 또는 메틸기를 나타내고,
L은 적어도 1개의 치환기를 가질 수도 있는 2가의 방향족 기, -C(=O)-O-기 또는 -C(=O)-NH-기를 나타내고, 이 -C(=O)-O-기 또는 -C(=O)-NH-기의 탄소원자는 폴리머의 주쇄와 결합하는 것이며,
X는 수소원자, 또는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기 혹은 알콕시기를 나타내고, 이 알킬기는 적어도 1개의 수소원자가 할로겐원자 또는 하이드록시기로 치환될 수도 있다.)
이 코폴리머는,
L이 적어도 1개의 치환기를 가질 수도 있는 2가의 방향족 기를 나타내는 구조단위와,
L이 -C(=O)-O-기를 나타내는 구조단위 및 -C(=O)-NH-기를 나타내는 구조단위 중 적어도 하나를 가지며,
단 상기 식(A)로 표시되는 구조단위를 갖는 폴리머는, 적어도 1개의 하이드록시기 또는 카르복시기, 혹은 적어도 1개의 하이드록시기 또는 카르복시기와 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기를 함유하는,
레지스트 패턴 피복용 도포액.
Component A: a polymer containing at least one hydroxy group or carboxyl group,
B component: A-SO 3 H (in the formula, A is a straight or branched alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms, an aromatic group having at least one alkyl group or a fluorinated alkyl group as a substituent, or a substituent Sulfonic acid represented by an alicyclic group having 4 to 16 carbon atoms which may be), and
C component: At least one of R 1 -OR 2 and R 1 -C(=O)-R 2 (in the formula, R 1 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 3 to 16 carbon atoms , R 2 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms.), an organic solvent capable of dissolving the polymer;
As a coating liquid for coating a resist pattern containing,
The polymer as the component A is a copolymer having at least two types of structural units represented by the following formula (A),
(In the formula, R 0 represents a hydrogen atom or a methyl group,
L represents a divalent aromatic group that may have at least one substituent, a -C(=O)-O- group, or a -C(=O)-NH- group, and this -C(=O)-O- group or The carbon atom of the -C(=O)-NH- group is bonded to the main chain of the polymer,
X represents a hydrogen atom, or a linear or branched alkyl group or alkoxy group having 1 to 10 carbon atoms, and in this alkyl group, at least one hydrogen atom may be substituted with a halogen atom or a hydroxy group.)
This copolymer,
A structural unit in which L represents a divalent aromatic group which may have at least one substituent,
L has at least one of a structural unit representing a -C(=O)-O- group and a structural unit representing a -C(=O)-NH- group,
However, in the polymer having the structural unit represented by the above formula (A), at least one hydroxy group or carboxyl group, or at least one hydroxy group or carboxyl group and at least one hydrogen atom may be substituted with a halogen atom with a number of carbon atoms of 1 to Containing 10 linear or branched alkyl groups,
Coating liquid for coating resist patterns.
상기 L에 있어서의 2가의 방향족 기는 페닐렌기 또는 나프틸렌기인, 레지스트 패턴 피복용 도포액.
The method of claim 1,
The coating liquid for coating a resist pattern, wherein the divalent aromatic group in L is a phenylene group or a naphthylene group.
B성분: A-SO3H(식 중, A는 탄소원자수 1 내지 16의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 방향족기, 또는 치환기를 가질 수도 있는 탄소원자수 4 내지 16의 지환식 기를 나타낸다.)로 표시되는 설폰산, 그리고
C성분: R1-O-R2 및 R1-C(=O)-R2 중 적어도 하나(식 중, R1은 탄소원자수 3 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타내고, R2는 탄소원자수 1 내지 16의 직쇄상, 분지쇄상 또는 환상의 알킬기 혹은 불화알킬기를 나타낸다.)로 표시되는 화합물로 이루어진, 상기 폴리머를 용해가능한 유기용매,
를 포함하는 레지스트 패턴 피복용 도포액으로서,
상기 A성분인 폴리머가, 하기 식(1-1) 내지 식(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머, 혹은 하기 식(1-1)~식(1-4) 중 어느 하나로 표시되는 구조단위를 갖는 폴리머로서 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있는 탄소원자수 1 내지 10의 직쇄상 또는 분지쇄상의 알킬기를 함유하는 폴리머인, 레지스트 패턴 피복용 도포액.
(식 중, Ar1은 탄소원자수 6 내지 18의 방향족 환을 적어도 1개 포함하는 2가, 4가, 6가 또는 8가의 유기기를 나타내고, Ar2는 메틸렌기 또는 제3급 탄소원자를 개재하여 Ar1과 결합해 있는 탄소원자수 6 내지 18의 방향족 환을 포함하는 2가의 유기기를 나타내고, 상기 방향족 환 중 적어도 1개는 치환기로서 하이드록시기 및 카르복시기 중 적어도 하나를 가진다.)
Component A: a polymer containing at least one hydroxy group or carboxyl group,
B component: A-SO 3 H (in the formula, A is a straight or branched alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms, an aromatic group having at least one alkyl group or a fluorinated alkyl group as a substituent, or a substituent Sulfonic acid represented by an alicyclic group having 4 to 16 carbon atoms which may be), and
C component: At least one of R 1 -OR 2 and R 1 -C(=O)-R 2 (in the formula, R 1 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 3 to 16 carbon atoms , R 2 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 16 carbon atoms.), an organic solvent capable of dissolving the polymer;
As a coating liquid for coating a resist pattern containing,
The polymer as the component A is a polymer having a structural unit represented by any one of the following formulas (1-1) to (1-4), or one of the following formulas (1-1) to (1-4) A coating solution for coating a resist pattern, comprising a polymer having a structural unit represented by a polymer containing a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom.
(In the formula, Ar 1 represents a divalent, tetravalent, hexavalent or octavalent organic group containing at least one aromatic ring having 6 to 18 carbon atoms, and Ar 2 is Ar via a methylene group or a tertiary carbon atom. Represents a divalent organic group including an aromatic ring having 6 to 18 carbon atoms bonded to 1, and at least one of the aromatic rings has at least one of a hydroxy group and a carboxyl group as a substituent.)
상기 Ar1로 표시되는 2가, 4가, 6가 또는 8가의 유기기는 하기 식(2-1) 내지 식(2-5) 중 어느 하나로 표시되는 화합물의 방향족 환상의 임의의 2개소, 4개소, 6개소 또는 8개소로부터의 결합단을 갖는 기이며,
이 Ar2는 하기 식(3-1)로 표시되는 2가의 유기기 또는 하기 식(3-2)로 표시되는 2가의 유기기를 나타내는, 레지스트 패턴 피복용 도포액.
〔식 중, R3 내지 R14, R16 및 R17은 각각 독립적으로 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 또는 환상의 알킬기, 탄소원자수 1 내지 9의 직쇄상 또는 분지쇄상의 알콕시기, 할로겐원자, 니트로기, 시아노기, 아세톡시기, 메틸티오기, 또는 아미노기를 나타내고, 이 알킬기는 적어도 1개의 수소원자가 하이드록시기 또는 할로겐원자로 치환될 수도 있고, 이 아미노기는 적어도 1개의 수소원자가 탄소원자수 1 내지 3의 직쇄상 또는 분지쇄상의 알킬기로 치환될 수도 있고, T3 내지 T14, T16 및 T17은 각각 독립적으로 하이드록시기 또는 카르복시기를 나타내고, T15는 수소원자 또는 메틸기를 나타내고, Q1 및 Q2는 각각 독립적으로 단결합, 산소원자, 황원자, 설포닐기, 카르보닐기, 이미노기, 탄소원자수 6 내지 40의 아릴렌기, 또는 탄소원자수 1 내지 10의 직쇄상, 분지쇄상 혹은 환상의 알킬렌기를 나타내고, 이 알킬렌기는 적어도 1개의 수소원자가 할로겐원자로 치환될 수도 있고, m1 내지 m4는 각각 독립적으로 0 내지 2의 정수를 나타내고, r4, r5 및 r8 내지 r14는 각각 독립적으로 0 내지 2의 정수를 나타내고, t4, t5 및 t8 내지 t14는 각각 독립적으로 0 내지 2의 정수를 나타내고, r3, r6, r7 및 r17은 각각 독립적으로 0 내지 8의 정수를 나타내고, t3, t6, t7 및 t17은 각각 독립적으로 0 내지 8의 정수를 나타내고, r16은 0 내지 9의 정수를 나타내고, t16은 0 내지 9의 정수를 나타내고, r3과 t3의 합계, r4와 t4의 합계, r5와 t5의 합계, r6과 t6의 합계, r7과 t7의 합계, r8과 t8의 합계, r9와 t9의 합계, r10과 t10의 합계, r11과 t11의 합계, r12와 t12의 합계, r13과 t13의 합계, r14와 t14의 합계, r16과 t16의 합계, 및 r17과 t17의 합계는 각각 독립적으로 1 내지 10의 정수이다.〕
The method of claim 3,
The divalent, tetravalent, hexavalent, or octavalent organic group represented by Ar 1 is any two or four places of the aromatic ring of the compound represented by any one of the following formulas (2-1) to (2-5) , Is a group having a bonding end from 6 or 8 places,
Ar 2 represents a divalent organic group represented by the following formula (3-1) or a divalent organic group represented by the following formula (3-2), a coating solution for coating a resist pattern.
[In the formula, R 3 to R 14 , R 16 and R 17 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, Represents a halogen atom, a nitro group, a cyano group, an acetoxy group, a methylthio group, or an amino group, and in this alkyl group, at least one hydrogen atom may be substituted with a hydroxy group or a halogen atom, and this amino group is at least one hydrogen atom It may be substituted with a linear or branched alkyl group of 1 to 3 embroidery, T 3 to T 14 , T 16 and T 17 each independently represent a hydroxy group or a carboxyl group, and T 15 represents a hydrogen atom or a methyl group , Q 1 and Q 2 are each independently a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, or a straight chain, branched chain or cyclic group having 1 to 10 carbon atoms. Represents an alkylene group, at least one hydrogen atom may be substituted with a halogen atom, m1 to m4 each independently represent an integer of 0 to 2, and r4, r5 and r8 to r14 are each independently 0 to 2 Represents the integer of, t4, t5 and t8 to t14 each independently represent an integer of 0 to 2, r3, r6, r7 and r17 each independently represent an integer of 0 to 8, and t3, t6, t7 and t17 Each independently represents an integer of 0 to 8, r16 represents an integer of 0 to 9, t16 represents an integer of 0 to 9, the sum of r3 and t3, the sum of r4 and t4, the sum of r5 and t5, Sum of r6 and t6, sum of r7 and t7, sum of r8 and t8, sum of r9 and t9, sum of r10 and t10, sum of r11 and t11, sum of r12 and t12, sum of r13 and t13, r14 and The sum of t14, the sum of r16 and t16, and the sum of r17 and t17 are each independently an integer of 1 to 10.]
상기 A성분인 폴리머가, 1000 내지 20000의 중량평균 분자량을 갖는, 레지스트 패턴 피복용 도포액.
The method according to claim 3 or 4,
The coating liquid for coating a resist pattern, wherein the polymer which is the component A has a weight average molecular weight of 1000 to 20000.
상기 A성분인 폴리머가, 1000 내지 2000의 중량평균 분자량을 갖는, 레지스트 패턴 피복용 도포액.
The method according to claim 1 or 2,
The coating solution for coating a resist pattern, wherein the polymer as the component A has a weight average molecular weight of 1000 to 2000.
상기 설폰산을 나타내는 식 중, A에 있어서의 방향족 기는 페닐기 또는 나프틸기인, 레지스트 패턴 피복용 도포액.
The method according to any one of claims 1 to 4,
In the formula representing the sulfonic acid, the aromatic group in A is a phenyl group or a naphthyl group.
상기 설폰산을 나타내는 식 중, A로 표시되는 기는, 탄소원자수 4 내지 12의 직쇄상 또는 분지쇄상의 알킬기 혹은 불화알킬기, 또는 이 알킬기 혹은 불화알킬기를 치환기로서 적어도 1개 갖는 페닐기를 나타내고,
이 설폰산의 함유비율은 상기 A성분인 폴리머에 대하여 0.5질량% 내지 60질량%인,
레지스트 패턴 피복용 도포액.
The method of claim 7,
In the formula representing the above sulfonic acid, the group represented by A represents a linear or branched alkyl group or fluorinated alkyl group having 4 to 12 carbon atoms, or a phenyl group having at least one alkyl group or fluorinated alkyl group as a substituent,
The content ratio of this sulfonic acid is 0.5% by mass to 60% by mass based on the polymer as component A,
Coating liquid for coating resist patterns.
1질량ppm 내지 1질량%의 물을 포함하는, 레지스트 패턴 피복용 도포액.
The method according to any one of claims 1 to 4,
A coating liquid for coating a resist pattern containing 1 ppm by mass to 1% by mass of water.
상기 레지스트 패턴을 피복하도록 제1항 내지 제4항 중 어느 한 항에 기재된 레지스트 패턴 피복용 도포액을 도포하는 공정,
상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정,
상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정, 및
상기 피복막을 현상액으로 현상후의 레지스트 패턴을, 린스액으로 린스처리하는 공정
을 포함하는, 레지스트 패턴의 형성방법.
Forming a resist pattern on a substrate on which an underlayer film is formed,
A step of applying the coating liquid for coating a resist pattern according to any one of claims 1 to 4 so as to coat the resist pattern,
Forming a coating film on the surface of the resist pattern by heating the substrate coated with the resist pattern coating liquid at 50°C to 130°C,
After cooling the heated substrate, developing the coating film with a developer, and
Process of rinsing the resist pattern after developing the coating film with a developer with a rinse solution
Containing, a method of forming a resist pattern.
상기 레지스트 패턴을 피복하도록 제1항 내지 제4항 중 어느 한 항에 기재된 레지스트 패턴 피복용 도포액을 도포하는 공정,
상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정,
상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정,
상기 피복막을 현상액으로 현상후의 레지스트 패턴의 패턴간을 충전하도록, 폴리실록산과 물 및 알코올류 중 적어도 하나를 함유하는 용매를 포함하는 제2 도포액을 도포하는 공정,
상기 제2 도포액에 포함되는 폴리실록산 이외의 성분 및 상기 현상액을 제거하거나 또는 감소시켜 도막을 형성하는 공정,
상기 도막을 에치백하여 상기 현상액으로 현상후의 레지스트 패턴의 상면을 노출시키는 공정, 및
상면이 노출된 상기 레지스트 패턴을 제거하는 공정을 포함하는, 반전 패턴의 형성방법.
Forming a resist pattern on a substrate on which an underlayer film is formed,
A step of applying the coating liquid for coating a resist pattern according to any one of claims 1 to 4 so as to coat the resist pattern,
Forming a coating film on the surface of the resist pattern by heating the substrate coated with the resist pattern coating liquid at 50°C to 130°C,
After cooling the heated substrate, developing the coating film with a developer,
A step of applying a second coating solution containing a solvent containing at least one of polysiloxane and water and alcohols so as to fill the pattern of the resist pattern after development of the coating film with a developer,
A step of removing or reducing components other than polysiloxane contained in the second coating solution and the developer to form a coating film,
Etching back the coating film to expose the upper surface of the developed resist pattern with the developer, and
A method of forming an inversion pattern, comprising a step of removing the resist pattern from which an upper surface is exposed.
상기 레지스트 패턴을 피복하도록 제1항 내지 제4항 중 어느 한 항에 기재된 레지스트 패턴 피복용 도포액을 도포하는 공정,
상기 레지스트 패턴 피복용 도포액이 도포된 기판을 50℃내지 130℃에서 가열하여 상기 레지스트 패턴의 표면에 피복막을 형성하는 공정,
상기 가열된 기판을 냉각후, 상기 피복막을 현상액으로 현상하는 공정,
상기 피복막을 현상액으로 현상후의 레지스트 패턴을, 린스액으로 린스처리하는 공정,
상기 린스액으로 린스처리후의 레지스트 패턴의 패턴간을 충전하도록, 폴리실록산과 물 및 알코올류 중 적어도 하나를 함유하는 용매를 포함하는 제2 도포액을 도포하는 공정,
상기 제2 도포액에 포함되는 폴리실록산 이외의 성분 및 상기 린스액을 제거하거나 또는 감소시켜 도막을 형성하는 공정,
상기 도막을 에치백하여 상기 린스액으로 린스처리후의 레지스트 패턴의 상면을 노출시키는 공정, 및
상면이 노출된 상기 레지스트 패턴을 제거하는 공정을 포함하는, 반전 패턴의 형성방법.
Forming a resist pattern on a substrate on which an underlayer film is formed,
A step of applying the coating liquid for coating a resist pattern according to any one of claims 1 to 4 so as to coat the resist pattern,
Forming a coating film on the surface of the resist pattern by heating the substrate coated with the resist pattern coating liquid at 50°C to 130°C,
After cooling the heated substrate, developing the coating film with a developer,
A step of rinsing the resist pattern after developing the coating film with a developer with a rinse solution,
A step of applying a second coating liquid containing a solvent containing at least one of polysiloxane and water and alcohols so as to fill between patterns of the resist pattern after the rinse treatment with the rinse liquid,
A step of removing or reducing components other than polysiloxane contained in the second coating solution and the rinse solution to form a coating film,
Etching back the coating film to expose the upper surface of the resist pattern after the rinsing treatment with the rinse solution, and
A method of forming an inversion pattern, comprising a step of removing the resist pattern from which an upper surface is exposed.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014190849 | 2014-09-19 | ||
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| JP2014201382 | 2014-09-30 | ||
| JPJP-P-2014-201382 | 2014-09-30 | ||
| PCT/JP2015/076715 WO2016043317A1 (en) | 2014-09-19 | 2015-09-18 | Application solution for resist pattern coating |
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| KR20170057238A KR20170057238A (en) | 2017-05-24 |
| KR102203366B1 true KR102203366B1 (en) | 2021-01-15 |
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| US (1) | US10133178B2 (en) |
| JP (1) | JP6497527B2 (en) |
| KR (1) | KR102203366B1 (en) |
| CN (1) | CN106715619B (en) |
| SG (1) | SG11201702233SA (en) |
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| CN106662820B (en) * | 2014-07-15 | 2021-06-22 | 日产化学工业株式会社 | Composition for forming silicon-containing resist underlayer film having halosulfonylalkyl group |
| US9869933B2 (en) * | 2016-03-07 | 2018-01-16 | Rohm And Haas Electronic Materials Llc | Pattern trimming methods |
| WO2017169981A1 (en) * | 2016-03-30 | 2017-10-05 | 日産化学工業株式会社 | Aqueous solution for coating resist pattern and pattern formation method using same |
| TWI722135B (en) * | 2016-04-13 | 2021-03-21 | 日商迪愛生股份有限公司 | Novolac resin and resist material |
| JP7112023B2 (en) * | 2016-10-04 | 2022-08-03 | 日産化学株式会社 | Method for producing resist pattern coating composition using solvent substitution method |
| CN109806658B (en) * | 2017-11-20 | 2021-10-12 | 台湾积体电路制造股份有限公司 | Developing solution filtering system and method |
| KR20210064190A (en) * | 2018-09-25 | 2021-06-02 | 니폰 제온 가부시키가이샤 | Copolymer and positive resist composition |
| US11506981B2 (en) * | 2019-05-31 | 2022-11-22 | Rohm And Haas Electronic Materials Llc | Photoresist pattern trimming compositions and pattern formation methods |
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| KR101860385B1 (en) | 2009-06-19 | 2018-05-23 | 닛산 가가쿠 고교 가부시키 가이샤 | Carbazole novolak resin |
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| JP6497527B2 (en) | 2019-04-10 |
| WO2016043317A1 (en) | 2016-03-24 |
| CN106715619B (en) | 2020-02-07 |
| SG11201702233SA (en) | 2017-04-27 |
| KR20170057238A (en) | 2017-05-24 |
| JPWO2016043317A1 (en) | 2017-06-29 |
| TWI681021B (en) | 2020-01-01 |
| US20170293227A1 (en) | 2017-10-12 |
| TW201627419A (en) | 2016-08-01 |
| US10133178B2 (en) | 2018-11-20 |
| CN106715619A (en) | 2017-05-24 |
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